CN102312232A - Environment-friendly copper and copper alloy surface passivation treatment fluid and passivation treatment method - Google Patents
Environment-friendly copper and copper alloy surface passivation treatment fluid and passivation treatment method Download PDFInfo
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- CN102312232A CN102312232A CN201110212055A CN201110212055A CN102312232A CN 102312232 A CN102312232 A CN 102312232A CN 201110212055 A CN201110212055 A CN 201110212055A CN 201110212055 A CN201110212055 A CN 201110212055A CN 102312232 A CN102312232 A CN 102312232A
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Abstract
The invention discloses an environment-friendly copper and copper alloy surface passivation treatment fluid and its passivation treatment method. Water or ethanol is used as a solvent of the passivation treatment fluid and its solute contains an N-C heterocycle compound; when the solvent is water, the solute also contains at least one component selected from a carboxylic acid compound and pyrophosphate; and when the solvent is ethanol, the solute also contains at least one component selected from a thio-alcohol compound, a carboxylic acid compound and pyrophosphate. In comparison with the prior art, by the principle of combining large molecular weight solute molecules and small molecular weight solute molecules together for self assembly on the surface of copper and copper alloy, the passivation treatment fluid provided by the invention has a much better passivation effect than a passivation treatment fluid, the solute of which is a single N-C heterocyclic compound, contains no substances of polluting the environment and influencing the health of human body, is convenient to use, requires low price, and has a good application prospect in the market.
Description
Technical field
The present invention relates to the metal material surface processing technology field, be specifically related to the inactivating treatment liquid and the deactivating process of treating thereof of a kind of environment-friendly type copper and copper alloy surface.
Background technology
China's copper and copper alloy amount of finish are annual about 1,000 ten thousand tons, and its annual output value is greater than 6,000 hundred million yuan.Generally, behind machined copper and the copper alloy workpiece, need carry out Passivation Treatment, to improve its anti-variable color and corrosion resistance to it.At present; Copper and copper alloy products passivation mainly adopt treatment solution such as chromic acid or its mixture to clean; But be to use these treatment solutions to carry out containing hexavalent chromium in the waste water after Cleaning and Passivation is handled, serious environment pollution with influence health of operators.Therefore, how eliminating the hexavalent chromium in the waste water after the passivation, is the key issue that copper and copper alloy surface treatment technology need solve.
At present, the method for environment-friendly type copper and copper alloy surface passivation is also had report, for example application number be the patent of invention of CN86103910.6 to adopt benzotriazole and Z 150PH be passivator, but this patent has still been used a spot 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 Hydrocerol A) 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 a passivator, but need under certain impressed voltage, carry out; Application number is that the patent of invention of CN201010595972.1 adopts mixed solutions such as phytic acid, ydrogen peroxide 50, boric acid, polyoxyethylene glycol that brass is carried out passivation; But this method is very complicated with sample ingredient; And phosphorus content is very high in the phytic acid (phytinic acid), can cause the chemical oxygen demand (COD) in the waste water to increase.
Summary of the invention
Technical purpose of the present invention is to 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 of treating of this inactivating treatment liquid to copper and copper alloy surface, and this inactivating treatment liquid has advantages such as the material, the passivation effect that do not contain contaminate environment and influence HUMAN HEALTH be good, easy to use, cheap.
The present invention realizes that the technical scheme that above-mentioned technical purpose adopts is: the inactivating treatment liquid of a kind of environment-friendly type copper and copper alloy surface; Its solvent is water or ethanol; Solute includes the N-C heterocyclic compound; It is characterized in that: when solvent is water, also include at least a in carboxylic acid compound and the pyrophosphate salt in the solute; When solvent is ethanol, also include at least a in sulfur alcohol compound and the carboxylic acid compound in the solute.
In the technique scheme:
Described N-C heterocyclic compound is preferably at least a in benzotriazole and the oxine;
Described sulfur alcohol compound is preferably at least a in 1.2-dithioglycol, propane thiol and the Dodecyl Mercaptan;
Described carboxylic acid compound is preferably at least a in formic acid, acetate, oxalic acid, propionic acid, butyric acid, formate, acetate, oxalate, propionic salt and the butyrates;
The pH value scope of described inactivating treatment liquid is preferably 2～7.
In the described inactivating treatment liquid, when solvent was water, the concentration range of benzotriazole was preferably the saturation concentration of 1g/l to benzotriazole, further was preferably 10g/l～19g/l; The concentration range of carboxylic acid compound is 1g/l～20g/l, further is preferably 5g/l～15g/l; The concentration range of pyrophosphate salt is 1g/l～20g/l, further is preferably 1g/l～5g/l.
In the described inactivating treatment liquid, when solvent is ethanol, the concentration range of oxine be 0.1g/l to its saturation concentration, further be preferably 1g/l～5g/l; The concentration of sulfur alcohol compound is 0.1g/l～1g/l, further is preferably 0.5g/l～1g/l.
The method of using inactivating treatment liquid of the present invention to handle copper and copper alloy surface specifically comprises the steps:
The configuration of step 1, inactivating treatment liquid:
The solute that will include the N-C heterocyclic compound is soluble in water, adds carboxylic acid compound and/or pyrophosphate salt then, obtains inactivating treatment liquid; Perhaps,
The solute that will include the N-C heterocyclic compound is dissolved in the alcohol solvent, adds sulfur alcohol compound and/or carboxylic acid compound then, obtains inactivating treatment liquid;
The surface degreasing of step 2, copper and copper alloy:
At mass percent concentration 5%～20% NaOH solution; Be to add an amount of sodium lauryl sulphate in 5%～20% the KOH solution perhaps at mass percent concentration; Obtain mixing solutions; Copper or copper alloy are put into this mixing solutions, be 40 ℃～70 ℃ at cleaning temperature and cleaned 3 minutes～10 minutes down;
Wherein, the concentration of sodium lauryl sulphate in mixing solutions is preferably 0.5g/l～10g/l, further is preferably 2g/l; Cleaning temperature is preferably 60 ℃～70 ℃;
The surperficial oxide film dissolving of step 3, copper and copper alloy is handled:
Utilize mechanical polishing, chemical rightenning or number of patent application copper or copper alloy to be carried out surface film oxide removal processing for the method described in the CN201110108791.6;
Wherein, number of patent application is among the CN201110108791.6, and the treatment process of removing copper and copper alloy surface sull with the treatment solution reduction specifically comprises the steps:
(1) configuration of treatment solution: reductive agent added form treatment solution in the entry; Described reductive agent is one or more the mixture in xitix, hypophosphite, glucose, hydrazine and verivate thereof, azanol and the verivate thereof, and the pH value of regulating treatment solution is 2～13;
(2) surface reduction of copper and copper alloy is handled: the treatment solution temperature is a normal temperature to 90 ℃, and copper after step 2 oil removing and copper alloy are immersed in the treatment solution, treats that surface reduction is to take out after copper and the copper alloy true qualities, cleans then, drying.
Hydrazine and verivate 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 verivate thereof include but not limited to N, N-diethyl hydroxylamine, N, N-dimethyl hydroxylamine, hydroxylamine phosphate, Acetohydroxamic Acid, oxammonium sulfate, hydroxylamine chloride.
Step 4, copper and copper alloy surface Passivation Treatment:
The inactivating treatment liquid that copper after step 3 handled or copper alloy are put into step 1 preparation carries out surface passivation to be handled.
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; Wherein solute ability and copper and copper alloy generation self-assembling reaction; In copper and the fine and close characteristic of copper alloy surface self-assembly one deck, thereby realize passivation effect to copper and copper alloy surface.Innovation part of the present invention is that this solute not only includes the N-C heterogeneous ring compound, also includes at least a in carboxylic acid compound, sulfur alcohol compound and the pyrophosphate salt.Because the molecular weight of each solute varies in size, 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 the passivation effect of copper and copper alloy surface on the whole.Especially when the molecular weight of each solute in the inactivating treatment liquid differs big; The bigger solute of molecular weight is in copper and the bigger characteristic of copper alloy surface self-assembly one deck molecular weight; This characteristic little spaces are arranged between molecule and the molecule unavoidably, and the less solute of molecular weight can be assembled among these spaces because molecular chain is longer; To fill up these little spaces; Thereby form the fine and close characteristic of one deck at copper and copper alloy surface, make copper and copper alloy and outside air and water isolated, improved copper and copper alloy surface passivation, erosion-resisting effect.
Color has considerable change when copper generation oxidation, brass deepening, red copper blackening.The experiment proof:
Existing, the two weeks left and right sides gloss in malaria of the brass after overpickling and polished finish can disappear, and three days color relations of red copper can change; Especially bigger in humidity; Under the higher environment of temperature, its color disintegration rate is faster, for example is 80% in humidity, temperature is under 70 ℃～90 ℃ the condition; The brass color and luster hold-time, the red copper color and luster hold-time was less than 2 hours less than 5 hours;
Existing, after overpickling and polished finish, be that the brass that the inactivating treatment liquid of single N-C heterogeneous ring compound is handled can disappear through about 1 month gloss in malaria through solute again; And red copper can change through all color relations, and is especially bigger in humidity, under the higher environment of temperature; Its color disintegration rate is faster; For example be 80% in humidity, temperature is that the brass color and luster hold-time, the red copper color and luster hold-time was less than 5 hours less than 50 hours under 70 ℃～90 ℃ the condition;
But in the present invention, after overpickling and polished finish, copper and the copper alloy after inactivating treatment liquid of the present invention is handled again has following effect:
(1) in malaria, brass nondiscoloration half a year, red copper nondiscoloration in three months;
(2) be 80% in humidity, temperature is under 70 ℃～90 ℃ the condition: the brass color and luster can keep more than 100 hours, and the 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 adopts the macromolecule solute molecule to combine the principle of the common self-assembly of small molecular weight solute molecule at copper and copper alloy surface, has following advantage:
(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 influence the material of HUMAN HEALTH, is a kind of inactivating treatment liquid of environment-friendly type, produces a large amount of sexavalent chromes when having avoided Passivation Treatment and problems such as contaminate environment and person health;
(3) easy to use, do not need after the passivation 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 good passivation.
Therefore, copper provided by the invention and copper alloy surface inactivating treatment liquid and deactivating process of treating thereof have advantages such as cost is low, easy to use, processing is rapid, effect is remarkable, environment protection health, have better market prospect.
Embodiment
Below through specific embodiment the present invention is done further explain, it is pointed out that the following stated embodiment is intended to be convenient to understanding of the present invention, and it does not played any qualification effect.
Following Passivation Treatment sample is the assembling red copper and cuts the copper alloy spray gun chewed and cut the brass spray gun of chewing with assembling brass.
Comparing embodiment 1:
In order to compare with following embodiment 1, among this comparative example the Passivation Treatment sample is only carried out surface cleaning and the processing of deoxidation film, do not use passivating solution to carry out Passivation Treatment.Concrete steps are:
(1) is to add the 2g/l sodium lauryl sulphate in 5%～20% the NaOH solution at mass percent concentration, obtains mixing solutions, the Passivation Treatment sample is put into this mixing solutions, be 60 ℃ at cleaning temperature and cleaned 5 minutes down;
(2) utilize the Passivation Treatment sample after mechanical polishing is handled step (2) to carry out surface film oxide removal processing.
The comparative example 2:
In order further to compare with following embodiment 1, the Passivation Treatment liquid formula is among this comparative example: solvent is a water, and solute is a benzotriazole, and the mass concentration of benzotriazole is 10g/l.
Use above-mentioned inactivating treatment liquid to be to the concrete steps that the Passivation Treatment sample surfaces carries out Passivation Treatment:
(1) an amount of benzotriazole is water-soluble, making the mass concentration of benzotriazole is 10g/l, obtains inactivating treatment liquid;
(2) be to add the 2g/l sodium lauryl sulphate in 5%～20% the NaOH solution at mass percent concentration, obtain mixing solutions, the Passivation Treatment sample is put into this mixing solutions, be 60 ℃ at cleaning temperature and cleaned 5 minutes down;
(3) utilize the Passivation Treatment sample after mechanical polishing is handled step (2) to carry out surface film oxide removal processing;
(4) the Passivation Treatment sample after step (3) is handled is dipped in the inactivating treatment liquid of step 1 preparation and carries out Passivation Treatment, and keeping the Passivation Treatment liquid temp is 60 ℃, and soak time is 5 minutes, handles the back 60 ℃ of oven dry 5 minutes.
Embodiment 1:
In the present embodiment:
The Passivation Treatment liquid formula is: solvent is a 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.
Use above-mentioned inactivating treatment liquid to be to the concrete steps that the Passivation Treatment sample surfaces carries out Passivation Treatment:
(1) an amount of benzotriazole is soluble in water, add an amount of propionic acid then, 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) be to add the 2g/l sodium lauryl sulphate in 5%～20% the NaOH solution at mass percent concentration, obtain mixing solutions, the Passivation Treatment sample is put into this mixing solutions, be 60 ℃ at cleaning temperature and cleaned 5 minutes down;
(3) utilize the Passivation Treatment sample after mechanical polishing is handled step (2) to carry out surface film oxide removal processing;
(4) the Passivation Treatment sample after step (3) is handled is dipped in the inactivating treatment liquid of step 1 preparation and carries out Passivation Treatment, and keeping the Passivation Treatment liquid temp is 60 ℃, and soak time is 5 minutes, handles the back 60 ℃ of oven dry 5 minutes.
Embodiment 2:
In the present embodiment:
The Passivation Treatment liquid formula is: solvent is an 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.
Use above-mentioned inactivating treatment liquid to be to the concrete steps that the Passivation Treatment sample surfaces carries out Passivation Treatment:
(1) an amount of benzotriazole is dissolved in the ethanol, adds an amount of Dodecyl Mercaptan then, 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) be to add the 2g/l sodium lauryl sulphate in 5%～20% the NaOH solution at mass percent concentration, the Passivation Treatment sample is put into this mixing solutions, be 40 ℃ at cleaning temperature and cleaned 10 minutes down;
(3) utilize the Passivation Treatment sample after chemical rightenning is handled step (2) to carry out surface film oxide removal processing;
(4) the Passivation Treatment sample after step (3) is handled is dipped in the inactivating treatment liquid of step 1 preparation and carries out Passivation Treatment, and keeping the Passivation Treatment liquid temp is 60 ℃, and soak time is 5 minutes, handles the back 60 ℃ of oven dry 5 minutes.
Instance 3:
In the present embodiment:
The Passivation Treatment liquid formula is: solvent is a 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.
Use above-mentioned inactivating treatment liquid to be to the concrete steps that the Passivation Treatment sample surfaces carries out Passivation Treatment:
(1) an amount of benzotriazole is dissolved in the ethanol, adds an amount of tetra-sodium then, 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) be to add the 2g/l sodium lauryl sulphate in 5%～20% the NaOH solution at mass percent concentration, obtain mixing solutions, the Passivation Treatment sample is put into this mixing solutions, be 70 ℃ at cleaning temperature and cleaned 3 minutes down;
(3) utilize number of patent application the Passivation Treatment sample to be carried out surface film oxide and remove processing for the method described in the CN201110108791.6;
(4) the Passivation Treatment sample after step (3) is handled is dipped in the inactivating treatment liquid of step 1 preparation and carries out Passivation Treatment, and keeping the Passivation Treatment liquid temp is 60 ℃, and soak time is 5 minutes, handles the back 60 ℃ of oven dry 5 minutes.
The comparative example 3:
In order to compare with following examples 4, the Passivation Treatment liquid formula is among this comparative example: solvent is an ethanol, and solute is an oxine, and the mass concentration of oxine is 2g/l.
Use above-mentioned inactivating treatment liquid to be to the concrete steps that the Passivation Treatment sample surfaces carries out Passivation Treatment:
(1) an amount of oxine is water-soluble, making the mass concentration of oxine is 2g/l, obtains inactivating treatment liquid;
(2) be to add the 2g/l sodium lauryl sulphate in 5%～20% the KOH solution at mass percent concentration, obtain mixing solutions, the Passivation Treatment sample is put into this mixing solutions, be 60 ℃ at cleaning temperature and cleaned 5 minutes down;
(3) utilize the Passivation Treatment sample after mechanical polishing is handled step (2) to carry out surface film oxide removal processing;
(4) the Passivation Treatment sample after step (3) is handled is dipped in the inactivating treatment liquid of step 1 preparation and carries out Passivation Treatment, and keeping the Passivation Treatment liquid temp is 60 ℃, and soak time is 5 minutes, handles the back 60 ℃ of oven dry 5 minutes.
Embodiment 4:
In the present embodiment:
The Passivation Treatment liquid formula is: solvent is an 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.
Use above-mentioned inactivating treatment liquid to be to the concrete steps that the Passivation Treatment sample surfaces carries out Passivation Treatment:
(1) an amount of oxine is soluble in water, add an amount of propionic acid then, 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) be to add the 2g/l sodium lauryl sulphate in 5%～20% the KOH solution at mass percent concentration, obtain mixing solutions, the Passivation Treatment sample is put into this mixing solutions, be 60 ℃ at cleaning temperature and cleaned 5 minutes down;
(3) utilize the Passivation Treatment sample after mechanical polishing is handled step (2) to carry out surface film oxide removal processing;
(4) the Passivation Treatment sample after step (3) is handled is dipped in the inactivating treatment liquid of step 1 preparation and carries out Passivation Treatment, and keeping the Passivation Treatment liquid temp is 60 ℃, and soak time is 5 minutes, handles the back 60 ℃ of oven dry 5 minutes.
Embodiment 5:
In the present embodiment:
The Passivation Treatment liquid formula is: solvent is an 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.
Use above-mentioned inactivating treatment liquid to be to the concrete steps that the Passivation Treatment sample surfaces carries out Passivation Treatment:
(1) an amount of oxine is soluble in water, add an amount of Dodecyl Mercaptan then, 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) be to add the 2g/l sodium lauryl sulphate in 5%～20% the KOH solution at mass percent concentration, obtain mixing solutions, the Passivation Treatment sample is put into this mixing solutions, be 60 ℃ at cleaning temperature and cleaned 5 minutes down;
(3) utilize the Passivation Treatment sample after mechanical polishing is handled step (2) to carry out surface film oxide removal processing;
(4) the Passivation Treatment sample after step (3) is handled is dipped in the inactivating treatment liquid of step 1 preparation and carries out Passivation Treatment, and keeping the Passivation Treatment liquid temp is 60 ℃, and soak time is 5 minutes, handles the back 60 ℃ of oven dry 5 minutes.
With the Passivation Treatment sample after handling among above-mentioned each embodiment be 80% in humidity, temperature is to test under 90 ℃ the condition, obtains result shown in the following table:
Sample in above each embodiment after the Passivation Treatment is 80% in humidity; Temperature is the interior baking of 70 ℃ baking oven; Observe the Passivation Treatment sample; Promptly assemble red copper and cut the copper alloy spray gun chewed and cut the brass spray gun of chewing with assembling brass and begin to occur the needed time of variable color, the result who obtains is as shown in the table.
Above-described embodiment specifies technical scheme of the present invention and beneficial effect; Be understood that the above is merely specific embodiment of the present invention; Be not limited to the present invention; The all any modifications in principle scope of the present invention, made and improvement etc. all should be included within protection scope of the present invention.
Claims (10)
1. the inactivating treatment liquid of environment-friendly type copper and copper alloy surface, its solvent is water or ethanol, solute includes the N-C heterocyclic compound, it is characterized in that: when solvent is water, also include at least a in carboxylic acid compound and the pyrophosphate salt in the solute; When solvent is ethanol, also include at least a in sulfur alcohol compound, carboxylic acid compound and the pyrophosphate salt in the solute.
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 a in benzotriazole and the oxine.
3. the inactivating treatment liquid of environment-friendly type copper according to claim 1 and copper alloy surface is characterized in that: described sulfur alcohol compound is at least a in 1.2-dithioglycol, propane thiol and the Dodecyl Mercaptan.
4. the inactivating treatment liquid of environment-friendly type copper according to claim 1 and copper alloy surface is characterized in that: described carboxylic acid compound is at least a in formic acid, acetate, oxalic acid, propionic acid, butyric acid, formate, acetate, oxalate, propionic salt and the butyrates.
5. 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.
6. the inactivating treatment liquid of environment-friendly type copper according to claim 2 and copper alloy surface; It is characterized in that: in the described inactivating treatment liquid; When solvent is water; The concentration range of benzotriazole is the saturation concentration of 1g/l to benzotriazole, and the concentration range of carboxylic acid compound is 1g/l～20g/l, and the concentration range of pyrophosphate salt is 1g/l～20g/l.
7. the inactivating treatment liquid of environment-friendly type copper according to claim 6 and copper alloy surface; It is characterized in that: in the described inactivating treatment liquid; The concentration range of benzotriazole is 10g/l～19g/l; The concentration range of carboxylic acid compound is 5～15g/l, and the concentration range of pyrophosphate salt is 1g/l～5g/l.
8. the inactivating treatment liquid of environment-friendly type copper according to claim 2 and copper alloy surface; It is characterized in that: in the described inactivating treatment liquid; When solvent is ethanol, the concentration range of oxine be 0.1g/l to its saturation concentration, the concentration of sulfur alcohol compound is 0.1g/l～1g/l.
9. the inactivating treatment liquid of environment-friendly type copper according to claim 8 and copper alloy surface is characterized in that: in the described inactivating treatment liquid, the concentration range of oxine is 1g/l～5g/l, and the concentration of sulfur alcohol compound is 0.5g/l～1g/l.
10. the method for described inactivating treatment liquid processing copper of arbitrary claim and copper alloy surface in the use claim 1 to 9 is characterized in that: comprise the steps:
The configuration of step 1, inactivating treatment liquid:
The solute that will include the N-C heterocyclic compound is soluble in water, adds carboxylic acid compound and/or pyrophosphate salt then, obtains inactivating treatment liquid; Perhaps,
The solute that will include the N-C heterocyclic compound is dissolved in the alcohol solvent, adds at least a in sulfur alcohol compound, carboxylic acid compound and the pyrophosphate salt then, obtains inactivating treatment liquid;
The surface degreasing of step 2, copper and copper alloy:
At mass percent concentration 5%～20% NaOH solution; Be to add an amount of sodium lauryl sulphate in 5%～20% the KOH solution perhaps at mass percent concentration; Obtain mixing solutions; Copper or copper alloy are put into this mixing solutions, be 40 ℃～70 ℃ in temperature and cleaned 3 minutes～10 minutes down;
The surperficial oxide film dissolving of step 3, copper and copper alloy is handled:
Utilize mechanical polishing, chemical rightenning or number of patent application copper and copper alloy to be carried out the oxide film dissolving processing for the method described in the CN201110108791.6;
Step 4, copper and copper alloy surface Passivation Treatment:
The inactivating treatment liquid that copper after step 3 handled or copper alloy are put into step 1 preparation carries out surface passivation to be handled.
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| CN103194744A (en) * | 2013-04-22 | 2013-07-10 | 江西铜业股份有限公司 | Copper foil surface passivation liquid and treatment method thereof, and treated copper foil |
| CN104818480A (en) * | 2015-04-28 | 2015-08-05 | 太仓市林源电线电缆有限公司 | Protective agent for braided copper wire |
| CN104911575A (en) * | 2015-06-13 | 2015-09-16 | 周彩球 | Environment-friendly copper part passivating agent |
| CN105024081A (en) * | 2015-07-07 | 2015-11-04 | 安徽铜冠铜箔有限公司 | Novel anti-oxidation liquid for copper foil of lithium ion battery |
| CN105839093A (en) * | 2016-05-31 | 2016-08-10 | 太原工业学院 | Normal-temperature chromium-free passivation liquid for electroplated copper and passivation technology of normal-temperature chromium-free passivation liquid |
| 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 |
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| CN107475723A (en) * | 2017-08-28 | 2017-12-15 | 厦门大学 | A kind of preparation method of corrosion-resistant copper electric wire |
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| WO2019042159A1 (en) * | 2017-08-28 | 2019-03-07 | 厦门大学 | Anticorrosion treatment method for copper-containing material |
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| 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 |
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| CN104818480A (en) * | 2015-04-28 | 2015-08-05 | 太仓市林源电线电缆有限公司 | Protective agent for braided copper wire |
| CN104911575A (en) * | 2015-06-13 | 2015-09-16 | 周彩球 | Environment-friendly copper part passivating agent |
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| CN105839093A (en) * | 2016-05-31 | 2016-08-10 | 太原工业学院 | Normal-temperature chromium-free passivation liquid for electroplated copper and passivation technology of normal-temperature chromium-free passivation liquid |
| 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 |
| 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 |
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| CN107365989A (en) * | 2017-07-11 | 2017-11-21 | 东莞市富默克化工有限公司 | A kind of metal surface treating method and its obtained metal protective film |
| CN107475700A (en) * | 2017-08-28 | 2017-12-15 | 厦门大学 | A kind of corrosion resistant copper alloy surface processing method |
| CN107475723A (en) * | 2017-08-28 | 2017-12-15 | 厦门大学 | A kind of preparation method of corrosion-resistant copper electric wire |
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| CN107475700B (en) * | 2017-08-28 | 2019-11-01 | 厦门大学 | A kind of corrosion resistant copper alloy surface processing method |
| CN107475723B (en) * | 2017-08-28 | 2019-11-01 | 厦门大学 | A kind of preparation method of corrosion-resistant copper electric wire |
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| 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 |
|---|---|
| CN103556142A (en) | 2014-02-05 |
| CN102312232B (en) | 2013-11-13 |
| CN103556142B (en) | 2016-05-11 |
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