CN103556142A - Passivation liquid for environment-friendly copper and copper alloy surface and passivation method - Google Patents
Passivation liquid for environment-friendly copper and copper alloy surface and passivation method Download PDFInfo
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Abstract
The invention discloses a passivation liquid for environment-friendly copper and copper alloy surface and a passivation method. The passivation liquid adopts water or ethanol as a solvent, solvend contains an N-C heterocyclic compound, when the solvent is water, the solvend also contains at least one of carboxylic-acid compound and pyrophosphate; when the solvent is ethanol, the solvend also contains at least one of mercaptan compound, carboxylic-acid compound and pyrophosphate. Compared with the prior art, the large-molecular-weight solvent molecules are combined with the small-molecular-weight solvend molecules to be collectively assembled on the surface of the copper and copper alloy, so that the passivation liquid has the advantages that the passivation effect is far better than that of the passivation liquid only with single N-C heterocyclic compound as solvend, no substance polluting the environment and influencing the health of the human body is contained, the use is convenient, the price is low and the like and the market application prospect is good.
Description
Technical field
The present invention relates to metal material surface processing technology field, be specifically related to inactivating treatment liquid and the deactivating process for the treatment of thereof of a kind of environment-friendly type copper and copper alloy surface.
Background technology
China Copper and copper alloy amount of finish are annual 1000 ten thousand tons of left and right, and its every annual value of production is greater than 6,000 hundred million yuan.Generally, after machined copper and copper alloy workpiece, need to carry out Passivation Treatment to it, to improve its resistance to variable color and corrosion resistance.At present, copper and copper alloy products passivation mainly adopt the treatment solutions such as chromic acid or its mixture to clean, but use these treatment solutions to carry out containing hexavalent chromium in the waste water after Cleaning and Passivation processing, serious environment pollution and affect the healthy of operator.Therefore, how eliminating the hexavalent chromium in waste water after passivation, is the key issue that copper and copper alloy surface treatment technology need to solve.
At present, the method for environment-friendly type copper and copper alloy surface passivation is also had to report, it is passivator that the patent of invention that for example application number is CN86103910.6 adopts benzotriazole and polyvinyl alcohol, but this patent has still been used a small amount of chromic acid; Application number is that the patent of invention of CN200810187682.6 adopts benzotriazole 5-8g/l, 1-phenyl-5 mercapto tetrazole 2-4g/l, tartrate (or citric acid) 14-18g/l, Sodium orthomolybdate (or sodium wolframate) 2-4g/l, the mixed solution of sodium lauryl sulphate 0.5-1g/l carries out passivation to brass, but this passivating solution complicated component, and expensive Sodium orthomolybdate or sodium wolframate have been used; Application number is that the patent of invention employing phytic acid of CN201010217372.1 is passivator, but need under certain impressed voltage, carry out; Application number is that the patent of invention of CN201010595972.1 adopts the mixed solutions such as phytic acid, hydrogen peroxide, boric acid, polyoxyethylene glycol to carry out passivation to brass, but the method is very complicated with sample ingredient, and phosphorus content is very high in phytic acid (phytinic acid), can cause the chemical oxygen demand (COD) in waste water to increase.
Summary of the invention
Technical purpose of the present invention is for the above-mentioned state of the art, providing a kind of provides the inactivating treatment liquid of a kind of environment-friendly type copper and copper alloy surface and utilizes the deactivating process for the treatment of of this inactivating treatment liquid to copper and copper alloy surface, and this inactivating treatment liquid has not containing contaminate environment and affects the advantages such as material, the passivation effect of HUMAN HEALTH be good, easy to use, cheap.
The present invention realizes the technical scheme that above-mentioned technical purpose adopts: the inactivating treatment liquid of a kind of environment-friendly type copper and copper alloy surface, its solvent is water or ethanol, solute includes N-C heterocyclic compound, it is characterized in that: when solvent is water, in solute, also include at least one in carboxylic acid compound and pyrophosphate salt; When solvent is ethanol, in solute, also include at least one in sulfur alcohol compound and carboxylic acid compound.
In technique scheme:
Described N-C heterocyclic compound is preferably at least one in benzotriazole and oxine;
Described sulfur alcohol compound is preferably at least one in 1.2-dithioglycol, propane thiol and Dodecyl Mercaptan;
Described carboxylic acid compound is preferably at least one in formic acid, acetic acid, oxalic acid, propionic acid, butyric acid, formate, acetate, oxalate, propionic salt and butyrates;
The pH value scope of described inactivating treatment liquid is preferably 2～7.
In described inactivating treatment liquid, when solvent is water, the concentration range of benzotriazole is preferably 1g/l to the saturation concentration of benzotriazole, more preferably 10g/l～19g/l; The concentration range of carboxylic acid compound is 1g/l～20g/l, more preferably 5g/l～15g/l; The concentration range of pyrophosphate salt is 1g/l～20g/l, more preferably 1g/l～5g/l.
In described inactivating treatment liquid, when solvent is ethanol, the concentration range of oxine is that 0.1g/l is to its saturation concentration, more preferably 1g/l～5g/l; The concentration of sulfur alcohol compound is 0.1g/l～1g/l, more preferably 0.5g/l～1g/l.
The method of using inactivating treatment liquid of the present invention to process copper and copper alloy surface specifically comprises the steps:
The configuration of step 1, inactivating treatment liquid:
The solute that includes N-C heterocyclic compound is soluble in water, then add carboxylic acid compound and/or pyrophosphate salt, obtain inactivating treatment liquid; Or,
The solute that includes N-C heterocyclic compound is dissolved in alcohol solvent, then adds sulfur alcohol compound and/or carboxylic acid compound, obtain inactivating treatment liquid;
The surface degreasing of step 2, copper and copper alloy:
The NaOH solution that is 5%～20% at mass percent concentration, or add appropriate sodium lauryl sulphate in the KOH solution that is 5%～20% at mass percent concentration, obtain mixing solutions, copper or copper alloy are put into this mixing solutions, are at 40 ℃～70 ℃, to clean 3 minutes～10 minutes at cleaning temperature;
Wherein, the concentration of sodium lauryl sulphate in mixing solutions is preferably 0.5g/l～10g/l, more preferably 2g/l; Cleaning temperature is preferably 60 ℃～70 ℃;
The surperficial oxide film dissolving of step 3, copper and copper alloy is processed:
Utilize mechanical polishing, chemical rightenning or number of patent application copper or copper alloy to be carried out to surface film oxide Transformatin for the method described in CN201110108791.6;
Wherein, number of patent application is in CN201110108791.6, and the treatment process of removing copper and copper alloy surface oxide film with treatment solution reduction specifically comprises the steps:
(1) configuration for the treatment of solution: reductive agent is added to the water to formation processing liquid, described reductive agent is one or more the mixture in xitix, hypophosphite, glucose, hydrazine and derivative thereof, azanol and derivative thereof, and regulating the pH value for the treatment of solution is 2～13;
(2) surface reduction of copper and copper alloy is processed: treatment solution temperature is normal temperature to 90 ℃, and the copper after step 2 oil removing and copper alloy are immersed in treatment solution, after surface reduction is copper and copper alloy true qualities, takes out, and then cleans, is dried.
Hydrazine and derivative thereof described in above-mentioned (1) include but not limited to NH
2-NH
2, NH
2-NH
2h
2o, phenylhydrazine, R
1r
2n-NR
1r
2(R representation hydrocarbyl); Described azanol and derivative thereof include but not limited to N, N-diethyl hydroxylamine, N, N-dimethyl hydroxylamine, phosphatic hydroxylamine, Acetohydroxamic Acid, oxammonium sulfate, hydroxylamine chloride.
Step 4, copper and copper alloy surface Passivation Treatment:
The inactivating treatment liquid that copper after step 3 is processed or copper alloy are put into step 1 preparation carries out surface passivating treatment.
The inactivating treatment liquid of environment-friendly type copper provided by the invention and copper alloy surface is a kind of aqueous solution or ethanolic soln, solute energy and copper and copper alloy generation self-assembling reaction wherein, in the characteristic of copper and the densification of copper alloy surface self-assembly one deck, thereby realize the passivation effect to copper and copper alloy surface.Innovation of the present invention is, this solute not only includes N-C heterogeneous ring compound, also includes at least one in carboxylic acid compound, sulfur alcohol compound and pyrophosphate salt.Because the molecular size range of each solute is different, its self-assembly ability at copper and copper alloy surface is different, and the compactness extent of formed self assembled monolayer film is also different, thereby acts synergistically, and has improved on the whole the passivation effect of copper and copper alloy surface.When especially the molecular weight of the solute of each in inactivating treatment liquid differs larger, the larger solute of molecular weight is in copper and the larger characteristic of copper alloy surface self-assembly one deck molecular weight, this characteristic is because molecular chain is longer, between molecule and molecule, there are unavoidably some little spaces, and the solute of molecular weight can be assembled among these spaces, to fill up these little spaces, thereby the characteristic in copper and the densification of copper alloy surface formation one deck, make copper and copper alloy and outside air and water isolated, copper and copper alloy surface passivation have been improved, erosion-resisting effect.
When oxidation occurs copper, color has considerable change, and brass is dimmed, red copper blackening.Experimental results show that:
Existing, brass after overpickling and polished finish two weeks left and right gloss in malaria can disappear, and three days color relations of red copper can change, especially larger in humidity, under the higher environment of temperature, its color disintegration rate is faster, for example, in humidity, be 80%, temperature is under the condition of 70 ℃～90 ℃, the brass color and luster hold-time is less than 5 hours, and the red copper color and luster hold-time is less than 2 hours;
Existing, after overpickling and polished finish, the brass that the inactivating treatment liquid that is single N-C heterogeneous ring compound through solute is again processed in malaria through about 1 month gloss can disappear, and red copper can change through one week color relation, especially larger in humidity, under the higher environment of temperature, its color disintegration rate is faster, for example in humidity, be 80%, temperature is that under the condition of 70 ℃～90 ℃, the brass color and luster hold-time is less than 50 hours, the red copper color and luster hold-time is less than 5 hours;
But, in the present invention, after overpickling and polished finish, then copper and copper alloy after inactivating treatment liquid of the present invention is processed, there is following effect:
(1) in malaria, brass nondiscoloration half a year, red copper nondiscoloration in three months;
(2) in humidity, be 80%, temperature is under the condition of 70 ℃～90 ℃: brass color and luster can keep more than 100 hours, and red copper color and luster can keep more than 50 hours.
Therefore, compared with prior art, the inactivating treatment liquid of copper provided by the invention and copper alloy surface employing macromolecule solute molecule is the principle at copper and copper alloy surface in conjunction with the common self-assembly of small molecules amount solute molecule, and tool has the following advantages:
(1) passivation effect is far superior to the inactivating treatment liquid that solute is single N-C heterogeneous ring compound;
(2) not containing contaminate environment and affect the material of HUMAN HEALTH, is a kind of inactivating treatment liquid of environment-friendly type, produces a large amount of sexavalent chromes and the problems such as contaminate environment and person health while having avoided Passivation Treatment;
(3) easy to use, after passivation, do not need to clean, but directly dry water saving;
(4) cheap, consumption is few and effective;
(5) applied widely, not only can carry out Passivation Treatment to copper alloy, and red copper (fine copper) is also had to good passivation.
Therefore, copper provided by the invention and copper alloy surface inactivating treatment liquid and deactivating process for the treatment of thereof, have the advantages such as cost is low, easy to use, processing is rapid, effect is remarkable, environment protection health, has good market application foreground.
Embodiment
By specific embodiment, the present invention is described in further detail below, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and it is not played to any restriction effect.
Following Passivation Treatment sample is assembling red copper and cuts the copper alloy spray gun of chewing and assemble brass and cut the brass spray gun of chewing.
Comparing embodiment 1:
In order to contrast with following embodiment 1, in this comparative example, Passivation Treatment sample is only carried out to surface cleaning and the processing of deoxidation film, do not use passivating solution to carry out Passivation Treatment.Concrete steps are:
(1) in the NaOH solution that is 5%～20% at mass percent concentration, adding 2g/l sodium lauryl sulphate, obtain mixing solutions, Passivation Treatment sample is put into this mixing solutions, is at 60 ℃, to clean 5 minutes at cleaning temperature;
(2) utilize the Passivation Treatment sample after mechanical polishing is processed step (2) to carry out surface film oxide Transformatin.
Comparative example 2:
In order further to contrast with following embodiment 1, in this comparative example, Passivation Treatment liquid formula is: solvent is water, and solute is benzotriazole, and the mass concentration of benzotriazole is 10g/l.
The concrete steps of using above-mentioned inactivating treatment liquid to carry out Passivation Treatment to Passivation Treatment sample surfaces are:
(1) appropriate benzotriazole is water-soluble, making the mass concentration of benzotriazole is 10g/l, obtains inactivating treatment liquid;
(2) in the NaOH solution that is 5%～20% at mass percent concentration, adding 2g/l sodium lauryl sulphate, obtain mixing solutions, Passivation Treatment sample is put into this mixing solutions, is at 60 ℃, to clean 5 minutes at cleaning temperature;
(3) utilize the Passivation Treatment sample after mechanical polishing is processed step (2) to carry out surface film oxide Transformatin;
(4) the Passivation Treatment sample after step (3) is processed is dipped in the inactivating treatment liquid of step 1 preparation and carries out Passivation Treatment, and keeping Passivation Treatment liquid temp is 60 ℃, and soak time is 5 minutes, after processing, at 60 ℃, dries 5 minutes.
Embodiment 1:
In the present embodiment:
Passivation Treatment liquid formula is: solvent is water, and solute is benzotriazole and propionic acid, and wherein, the mass concentration of benzotriazole is 10g/l, and the mass concentration of propionic acid is 10g/l.
The concrete steps of using above-mentioned inactivating treatment liquid to carry out Passivation Treatment to Passivation Treatment sample surfaces are:
(1) appropriate benzotriazole is soluble in water, then add appropriate propionic acid, the mass concentration that makes benzotriazole is 10g/l, the mass concentration of propionic acid is 10g/l, makes to obtain inactivating treatment liquid;
(2) in the NaOH solution that is 5%～20% at mass percent concentration, adding 2g/l sodium lauryl sulphate, obtain mixing solutions, Passivation Treatment sample is put into this mixing solutions, is at 60 ℃, to clean 5 minutes at cleaning temperature;
(3) utilize the Passivation Treatment sample after mechanical polishing is processed step (2) to carry out surface film oxide Transformatin;
(4) the Passivation Treatment sample after step (3) is processed is dipped in the inactivating treatment liquid of step 1 preparation and carries out Passivation Treatment, and keeping Passivation Treatment liquid temp is 60 ℃, and soak time is 5 minutes, after processing, at 60 ℃, dries 5 minutes.
Embodiment 2:
In the present embodiment:
Passivation Treatment liquid formula is: solvent is ethanol, and solute is benzotriazole and Dodecyl Mercaptan, and wherein, the mass concentration of benzotriazole is 10g/l, and the mass concentration of Dodecyl Mercaptan is 1g/l.
The concrete steps of using above-mentioned inactivating treatment liquid to carry out Passivation Treatment to Passivation Treatment sample surfaces are:
(1) appropriate benzotriazole is dissolved in ethanol, then adds appropriate Dodecyl Mercaptan, the mass concentration that makes benzotriazole is 10g/l, and the mass concentration of Dodecyl Mercaptan is 1g/l, makes to obtain inactivating treatment liquid;
(2) in the NaOH solution that is 5%～20% at mass percent concentration, adding 2g/l sodium lauryl sulphate, Passivation Treatment sample is put into this mixing solutions, is at 40 ℃, to clean 10 minutes at cleaning temperature;
(3) utilize the Passivation Treatment sample after chemical rightenning is processed step (2) to carry out surface film oxide Transformatin;
(4) the Passivation Treatment sample after step (3) is processed is dipped in the inactivating treatment liquid of step 1 preparation and carries out Passivation Treatment, and keeping Passivation Treatment liquid temp is 60 ℃, and soak time is 5 minutes, after processing, at 60 ℃, dries 5 minutes.
Example 3:
In the present embodiment:
Passivation Treatment liquid formula is: solvent is water, and solute is benzotriazole and tetra-sodium, and wherein, the mass concentration of benzotriazole is 10g/l, and the mass concentration of tetra-sodium is 5g/l.
The concrete steps of using above-mentioned inactivating treatment liquid to carry out Passivation Treatment to Passivation Treatment sample surfaces are:
(1) appropriate benzotriazole is dissolved in ethanol, then adds appropriate tetra-sodium, the mass concentration that makes benzotriazole is 10g/l, and the mass concentration of tetra-sodium is 5g/l, makes to obtain inactivating treatment liquid;
(2) in the NaOH solution that is 5%～20% at mass percent concentration, adding 2g/l sodium lauryl sulphate, obtain mixing solutions, Passivation Treatment sample is put into this mixing solutions, is at 70 ℃, to clean 3 minutes at cleaning temperature;
(3) utilize number of patent application Passivation Treatment sample to be carried out to surface film oxide Transformatin for the method described in CN201110108791.6;
(4) the Passivation Treatment sample after step (3) is processed is dipped in the inactivating treatment liquid of step 1 preparation and carries out Passivation Treatment, and keeping Passivation Treatment liquid temp is 60 ℃, and soak time is 5 minutes, after processing, at 60 ℃, dries 5 minutes.
Comparative example 3:
In order to contrast with following examples 4, in this comparative example, Passivation Treatment liquid formula is: solvent is ethanol, and solute is oxine, and the mass concentration of oxine is 2g/l.
The concrete steps of using above-mentioned inactivating treatment liquid to carry out Passivation Treatment to Passivation Treatment sample surfaces are:
(1) appropriate oxine is water-soluble, making the mass concentration of oxine is 2g/l, obtains inactivating treatment liquid;
(2) in the KOH solution that is 5%～20% at mass percent concentration, adding 2g/l sodium lauryl sulphate, obtain mixing solutions, Passivation Treatment sample is put into this mixing solutions, is at 60 ℃, to clean 5 minutes at cleaning temperature;
(3) utilize the Passivation Treatment sample after mechanical polishing is processed step (2) to carry out surface film oxide Transformatin;
(4) the Passivation Treatment sample after step (3) is processed is dipped in the inactivating treatment liquid of step 1 preparation and carries out Passivation Treatment, and keeping Passivation Treatment liquid temp is 60 ℃, and soak time is 5 minutes, after processing, at 60 ℃, dries 5 minutes.
Embodiment 4:
In the present embodiment:
Passivation Treatment liquid formula is: solvent is ethanol, and solute is oxine and propionic acid, and wherein, the mass concentration of oxine is 2g/l, and the mass concentration of propionic acid is 10g/l.
The concrete steps of using above-mentioned inactivating treatment liquid to carry out Passivation Treatment to Passivation Treatment sample surfaces are:
(1) appropriate oxine is soluble in water, then add appropriate propionic acid, the mass concentration that makes oxine is 2g/l, the mass concentration of propionic acid is 10g/l, makes to obtain inactivating treatment liquid;
(2) in the KOH solution that is 5%～20% at mass percent concentration, adding 2g/l sodium lauryl sulphate, obtain mixing solutions, Passivation Treatment sample is put into this mixing solutions, is at 60 ℃, to clean 5 minutes at cleaning temperature;
(3) utilize the Passivation Treatment sample after mechanical polishing is processed step (2) to carry out surface film oxide Transformatin;
(4) the Passivation Treatment sample after step (3) is processed is dipped in the inactivating treatment liquid of step 1 preparation and carries out Passivation Treatment, and keeping Passivation Treatment liquid temp is 60 ℃, and soak time is 5 minutes, after processing, at 60 ℃, dries 5 minutes.
Embodiment 5:
In the present embodiment:
Passivation Treatment liquid formula is: solvent is ethanol, and solute is oxine and Dodecyl Mercaptan, and wherein, the mass concentration of oxine is 2g/l, and the mass concentration of Dodecyl Mercaptan is 1g/l.
The concrete steps of using above-mentioned inactivating treatment liquid to carry out Passivation Treatment to Passivation Treatment sample surfaces are:
(1) appropriate oxine is soluble in water, then add appropriate Dodecyl Mercaptan, the mass concentration that makes oxine is 2g/l, the mass concentration of Dodecyl Mercaptan is 10g/l, makes to obtain inactivating treatment liquid;
(2) in the KOH solution that is 5%～20% at mass percent concentration, adding 2g/l sodium lauryl sulphate, obtain mixing solutions, Passivation Treatment sample is put into this mixing solutions, is at 60 ℃, to clean 5 minutes at cleaning temperature;
(3) utilize the Passivation Treatment sample after mechanical polishing is processed step (2) to carry out surface film oxide Transformatin;
(4) the Passivation Treatment sample after step (3) is processed is dipped in the inactivating treatment liquid of step 1 preparation and carries out Passivation Treatment, and keeping Passivation Treatment liquid temp is 60 ℃, and soak time is 5 minutes, after processing, at 60 ℃, dries 5 minutes.
By the Passivation Treatment sample after processing in the various embodiments described above in humidity, be 80%, temperature is to test under the condition of 90 ℃, obtains result shown in following table:
Sample after Passivation Treatment in above each embodiment is 80% in humidity, temperature is the interior baking of the baking oven of 70 ℃, observe Passivation Treatment sample, assemble red copper and cut the copper alloy spray gun chewed and assembling brass and cut the brass spray gun of chewing and start to occur the needed time of variable color, the result obtaining is as shown in the table.
Above-described embodiment has been described in detail technical scheme of the present invention and beneficial effect; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all any modifications of making within the scope of principle of the present invention and improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. the inactivating treatment liquid of environment-friendly type copper and copper alloy surface, its solvent is water or ethanol, solute includes N-C heterocyclic compound, it is characterized in that: in solute, also include pyrophosphate salt.
2. the inactivating treatment liquid of environment-friendly type copper according to claim 1 and copper alloy surface, is characterized in that: described N-C heterocyclic compound is at least one in benzotriazole and oxine.
3. the inactivating treatment liquid of environment-friendly type copper according to claim 1 and copper alloy surface, is characterized in that: the pH value scope of described inactivating treatment liquid is 2～7.
4. the inactivating treatment liquid of environment-friendly type copper according to claim 2 and copper alloy surface, it is characterized in that: in described inactivating treatment liquid, when solvent is water, the concentration range of benzotriazole be 1g/l to the saturation concentration of benzotriazole, the concentration range of pyrophosphate salt is 1g/l～20g/l.
5. the inactivating treatment liquid of environment-friendly type copper according to claim 4 and copper alloy surface, is characterized in that: in described inactivating treatment liquid, the concentration range of benzotriazole is 10g/l～19g/l, and the concentration range of pyrophosphate salt is 1g/l～5g/l.
6. the inactivating treatment liquid processing copper described in arbitrary claim and the method for copper alloy surface in right to use requirement 1 to 5, is characterized in that: comprise the steps:
The configuration of step 1, inactivating treatment liquid:
The solute that includes N-C heterocyclic compound is soluble in water, then add pyrophosphate salt, obtain inactivating treatment liquid; Or,
The solute that includes N-C heterocyclic compound is dissolved in alcohol solvent, then adds pyrophosphate salt, obtain inactivating treatment liquid;
The surface degreasing of step 2, copper and copper alloy:
The NaOH solution that is 5%～20% at mass percent concentration, or add appropriate sodium lauryl sulphate in the KOH solution that is 5%～20% at mass percent concentration, obtain mixing solutions, copper or copper alloy are put into this mixing solutions, are at 40 ℃～70 ℃, to clean 3 minutes～10 minutes in temperature;
The surperficial oxide film dissolving of step 3, copper and copper alloy is processed:
Utilize mechanical polishing or chemical rightenning to carry out oxide film dissolving processing to copper and copper alloy;
Step 4, copper and copper alloy surface Passivation Treatment:
The inactivating treatment liquid that copper after step 3 is processed or copper alloy are put into step 1 preparation carries out surface passivating treatment.
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| CN101153205A (en) * | 2006-09-29 | 2008-04-02 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution for polishing low dielectric materials |
| CN101368273A (en) * | 2007-08-15 | 2009-02-18 | 江苏海迅实业集团股份有限公司 | Copper alloy antirust agent |
| CN101717619A (en) * | 2009-11-13 | 2010-06-02 | 广州大学 | Industrial low-temperature heat exchange secondary refrigerant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104625481A (en) * | 2014-12-31 | 2015-05-20 | 芜湖协诚金属制品有限公司 | Protective agent for welding spot in metal welding |
| CN107022756A (en) * | 2017-05-18 | 2017-08-08 | 依波精品（深圳）有限公司 | The passivation technology of silver and silver alloy |
| CN107022756B (en) * | 2017-05-18 | 2018-03-20 | 依波精品（深圳）有限公司 | The passivation technology of silver or silver alloy |
| CN112342534A (en) * | 2020-11-11 | 2021-02-09 | 桂林漓佳金属有限责任公司 | Passivating agent for passivating copper alloy surface |
Also Published As
| Publication number | Publication date |
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| CN103556142B (en) | 2016-05-11 |
| CN102312232A (en) | 2012-01-11 |
| CN102312232B (en) | 2013-11-13 |
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