CN103572306A - Deplating solution for removing nickel on cooper surface, preparation method thereof, and method for removing nickel on cooper surface - Google Patents
Deplating solution for removing nickel on cooper surface, preparation method thereof, and method for removing nickel on cooper surface Download PDFInfo
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- CN103572306A CN103572306A CN201210264913.5A CN201210264913A CN103572306A CN 103572306 A CN103572306 A CN 103572306A CN 201210264913 A CN201210264913 A CN 201210264913A CN 103572306 A CN103572306 A CN 103572306A
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- decoating liquid
- nickel
- sulfuric acid
- copper
- hydrogen peroxide
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Abstract
The invention provides a deplating solution for removing nickel on cooper surface. The deplating solution contains water solutions of following components: 100 to 200 g/L of sulfuric acid, 50 to 200 g/L of hydrogen peroxide, 90 to 270 g/L of ethene diamine, 5 to 50 g/L of cysteine, and 1 to 10 g/L of sulfamic acid. The invention also provides a preparation method of the deplating solution, and a method for removing nickel on cooper surface by using the deplating solution. The deplating solution provided by the invention is capable of carrying out a process on a tool to be deplated at a room temperature, barely no volatile irritant gas is generated during the deplating process, so the deplating solution is very environment-friendly; and at the same time, the quality and thickness of the copper layer, and the combining force between the copper layer and subsequent coating are not affected.
Description
Technical field
The invention belongs to chemical strip technical field, relate in particular to a kind of decoating liquid that moves back nickel for copper surface and preparation method thereof and a kind of method for the copper surface nickel of decorporating.
Background technology
Often need to be on metallic copper in modern electroplating technology metallizing nickel dam anticorrosion to play, antirust, or on metallic copper, plate other metal transfer coating.Because quality problems easily appear in nickel layer in copper plating nickel on surface process, therefore need to re-start again Nickel Plating Treatment after strip nickel dam.About coating withdrawal plating, generally can adopt the method for chemistry or electrochemistry stripping.Electrochemical method stripping liquid composition is simple, faint to base material corrosion, some metal recoverable is conducive to environment protection, but power supply and strip groove need to be provided, and sometimes needs special hanger, and this is disadvantageous for the workshop of not producing in enormous quantities.In addition, owing to being generally complex geometric shapes in waste material, in electrolytic removal process, be always difficult to guarantee all dissolved strippings and part is not corroded of low current density and high current density place coating, the application of electrochemistry stripping is limited greatly.
Therefore, in prior art, the general chemical dissolution method that adopts carries out strip.But common strip agent often also can be returned copper layer, causes product rejection.In current chemical strip method, conventional strip agent is the mixed system of potassium sulfocyanate and m-nitrobenzene sodium sulfonate, adopt on the one hand this strip agent to carry out can forming the film that one deck is difficult to wash off, the bonding force while affecting follow-up metal lining again between coating and copper at copper surface after strip processing; On the other hand, this strip agent temperature when strip raises, and produces volatility irritant gas larger to human injury.
Summary of the invention
The invention solves the harmful property of generation volatility irritant gas that strip agent that in prior art, chemical strip method is used exists, affect the quality of copper layer and subsequent plating layer and the technical problem of bonding force simultaneously.
The invention provides a kind of decoating liquid that moves back nickel for copper surface, in described decoating liquid, contain the aqueous solution of following component:
Sulfuric acid 100-200g/L;
Hydrogen peroxide 50-200g/L;
Quadrol 90-270g/L;
Halfcystine 5-50g/L;
Thionamic acid 1-10g/L.
The present invention also provides the preparation method of described decoating liquid, comprises sulfuric acid, hydrogen peroxide, quadrol, halfcystine, the thionamic acid formation aqueous solution soluble in water in proportion.
Finally, the invention provides a kind of method for the copper surface nickel of decorporating, comprise and will treat that strip workpiece impregnated in decoating liquid provided by the invention; Describedly treat that strip workpiece comprises metallic copper, this copper surface is laminated with metallic nickel.
Decoating liquid provided by the invention; by adopting the compound system of sulfuric acid and hydrogen peroxide as the oxygenant of metallic nickel; by quadrol and halfcystine coordinating protection metallic copper, exempt to be corroded simultaneously; and control by thionamic acid the speed that nickel is moved back in oxygenant dissolving, thereby the metallic nickel on copper surface thoroughly can be removed under the prerequisite not being corroded at protection copper.Adopting decoating liquid provided by the invention at room temperature can treat strip workpiece processes; and in strip process, produce hardly volatile irritating smell gas; very environmental protection, can not affect the quality of copper layer quality, thickness coating and the bonding force between copper layer and subsequent plating layer simultaneously.
Embodiment
The invention provides a kind of decoating liquid that moves back nickel for copper surface, in described decoating liquid, contain the aqueous solution of following component:
Sulfuric acid 100-200g/L;
Hydrogen peroxide 50-200g/L;
Quadrol 90-270g/L;
Halfcystine 5-50g/L;
Thionamic acid 1-10g/L.
Decoating liquid provided by the invention; by adopting the compound system of sulfuric acid and hydrogen peroxide as the oxygenant of metallic nickel; by quadrol and halfcystine coordinating protection metallic copper, exempt to be corroded simultaneously; and control by thionamic acid the speed that nickel is moved back in oxygenant dissolving, thereby the metallic nickel on copper surface thoroughly can be removed under the prerequisite not being corroded at protection copper.
As a kind of preferred implementation of the present invention, in described decoating liquid, each component concentration is:
Sulfuric acid 120-180g/L;
Hydrogen peroxide 80-150g/L;
Quadrol 120-240g/L;
Halfcystine 10-30g/L;
Thionamic acid 3-7g/L.
The present invention also provides the preparation method of described decoating liquid, comprises sulfuric acid, hydrogen peroxide, quadrol, halfcystine, the thionamic acid formation aqueous solution soluble in water in proportion.
Under preferable case, first prepare aqueous sulfuric acid, then in aqueous sulfuric acid, add successively hydrogen peroxide, quadrol and halfcystine, obtain mixed system; Thionamic acid is dissolved in the water and forms thionamic acid solution, then thionamic acid solution is mixed with mixed system, obtain described decoating liquid.
Finally, the invention provides a kind of method for the copper surface nickel of decorporating, comprise and will treat that strip workpiece impregnated in decoating liquid provided by the invention; Describedly treat that strip workpiece comprises metallic copper, this copper surface is laminated with metallic nickel.
For guaranteeing the homogeneity of metallic nickel strip, under preferable case, in described strip treating processes, also comprise the step that decoating liquid is stirred.
Method provided by the invention is applicable to the workpiece that various copper surface coverage have nickel, for example, in the present invention, described in treat that plastics part, surface that strip workpiece stacks gradually metallic copper and metallic nickel for surface stack gradually the ceramic workpiece of metallic copper and metallic nickel or the metallic copper workpiece that surface is laminated with metallic nickel.
Adopt decoating liquid provided by the invention at room temperature can treat strip workpiece and process, and in strip process, volatility is few, very environmental protection, can not affect the quality of copper layer quality, thickness coating and the bonding force between copper layer and subsequent plating layer simultaneously.While adopting decoating liquid provided by the invention to carry out strip processing to copper layer surface metal nickel dam, the temperature of decoating liquid and strip immersion treatment time can suitably be selected according to the concrete thickness of nickel dam.For example, when described metallic nickel is thickness while being the chemical Ni-plating layer of 1-10 micron, the temperature of described decoating liquid is 40-70 ℃, and dipping time is 5-10min.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
By following formula, first sulfuric acid is mixed with to the aqueous solution, thionamic acid is mixed with to the aqueous solution; Then in aqueous sulfuric acid, add successively hydrogen peroxide, quadrol and halfcystine, obtain mixed system; Then the thionamic acid aqueous solution is mixed with mixed system, obtain decoating liquid S1, in this decoating liquid S1, each component concentration is: sulfuric acid 150g/L, hydrogen peroxide 100g/L, quadrol 180g/L, halfcystine 7g/L, thionamic acid 5g/L.
Embodiment 2
By following formula, first sulfuric acid is mixed with to the aqueous solution, thionamic acid is mixed with to the aqueous solution; Then in aqueous sulfuric acid, add successively hydrogen peroxide, quadrol and halfcystine, obtain mixed system; Then the thionamic acid aqueous solution is mixed with mixed system, obtain decoating liquid S2, in this decoating liquid S2, each component concentration is: sulfuric acid 120g/L, hydrogen peroxide 90g/L, quadrol 135g/L, halfcystine 5g/L, thionamic acid 3g/L.
Embodiment 3
By following formula, first sulfuric acid is mixed with to the aqueous solution, thionamic acid is mixed with to the aqueous solution; Then in aqueous sulfuric acid, add successively hydrogen peroxide, quadrol and halfcystine, obtain mixed system; Then the thionamic acid aqueous solution is mixed with mixed system, obtain decoating liquid S3, in this decoating liquid S3, each component concentration is: sulfuric acid 100g/L, hydrogen peroxide 50g/L, quadrol 90g/L, halfcystine 5g/L.
Embodiment 4
By following formula, first sulfuric acid is mixed with to the aqueous solution, thionamic acid is mixed with to the aqueous solution; Then in aqueous sulfuric acid, add successively hydrogen peroxide, quadrol and halfcystine, obtain mixed system; Then the thionamic acid aqueous solution is mixed with mixed system, obtain decoating liquid S4, in this decoating liquid S4, each component concentration is: sulfuric acid 200g/L, hydrogen peroxide 200g/L, quadrol 270g/L, halfcystine 50g/L, thionamic acid 10g/L.
Comparative example 1
According to the following ratio sulfuric acid, hydrogen peroxide, halfcystine, thionamic acid are dissolved in the water: sulfuric acid 150g/L, hydrogen peroxide 100g/L, halfcystine 7g/L, thionamic acid 5g/L, obtains the decoating liquid DS1 of the present embodiment.
Comparative example 2
According to the following ratio sulfuric acid, hydrogen peroxide, quadrol, thionamic acid are dissolved in the water: sulfuric acid 150g/L, hydrogen peroxide 100g/L, quadrol 180g/L, thionamic acid 5g/L, obtains the decoating liquid DS2 of the present embodiment.
Comparative example 3
According to the following ratio sulfuric acid, hydrogen peroxide are dissolved in the water: sulfuric acid 150g/L, hydrogen peroxide 100g/L obtains the decoating liquid DS3 of the present embodiment.
Comparative example 1
According to the following ratio m-nitrobenzene sodium sulfonate, potassium sulfocyanate are dissolved in the water: m-nitrobenzene sodium sulfonate 60g/L, potassium sulfocyanate 1g/L obtains the decoating liquid DS4 of the present embodiment.
Performance test
The ABS plastic workpiece (surperficial nickel dam is that thickness is the chemical Ni-plating layer of 3 microns) that surface is coated with successively to copper layer and nickel dam impregnated in respectively in decoating liquid S1-S4 and DS1-DS4, constantly stirs decoating liquid in steeping process; Estimate to nickel dam by rear the taking-up workpiece, the time of recording each workpiece surface strip nickel dam of complete strip removal.Record the smell size of the irritant gas producing in strip process simultaneously, and observe after strip the workpiece surface metallic copper phenomenon that whether is corroded.
Test result is as shown in table 1.
Table 1
From the test result of upper table 1, can find out, adopt the decoating liquid that the present invention passes through the metallic nickel on copper surface thoroughly can be stripped, and do not corrode copper surface, in strip process, produce hardly volatile irritating smell gas simultaneously or produce less, very environmental protection.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. for copper surface, move back a decoating liquid for nickel, it is characterized in that, in described decoating liquid, contain the aqueous solution of following component:
Sulfuric acid 100-200g/L;
Hydrogen peroxide 50-200g/L;
Quadrol 90-270g/L;
Halfcystine 5-50g/L;
Thionamic acid 1-10g/L.
2. decoating liquid according to claim 1, is characterized in that, in described decoating liquid, each component concentration is:
Sulfuric acid 120-180g/L;
Hydrogen peroxide 80-150g/L;
Quadrol 120-240g/L;
Halfcystine 10-30g/L;
Thionamic acid 3-7g/L.
3. the preparation method of the decoating liquid described in claim 1 or 2, is characterized in that, comprises sulfuric acid, hydrogen peroxide, quadrol, halfcystine, the thionamic acid formation aqueous solution soluble in water in proportion.
4. preparation method according to claim 3, is characterized in that, comprises and first prepares aqueous sulfuric acid, then in aqueous sulfuric acid, adds successively hydrogen peroxide, quadrol and halfcystine, obtains mixed system; Thionamic acid is dissolved in the water and forms thionamic acid solution, then thionamic acid solution is mixed with mixed system, obtain described decoating liquid.
5. for a method for the copper surface nickel of decorporating, it is characterized in that, comprise and will treat that strip workpiece impregnated in the decoating liquid described in claim 1 or 2; Describedly treat that strip workpiece comprises metallic copper, this copper surface is laminated with metallic nickel.
6. method according to claim 5, is characterized in that, also comprises and will after strip workpiece impregnated in decoating liquid, stir the step of decoating liquid.
7. method according to claim 5, it is characterized in that, described in treat that plastics part, surface that strip workpiece stacks gradually metallic copper and metallic nickel for surface stack gradually the ceramic workpiece of metallic copper and metallic nickel or the metallic copper workpiece that surface is laminated with metallic nickel.
8. according to the method described in claim 5 or 7, described metallic nickel is that thickness is the chemical Ni-plating layer of 1-10 micron; The temperature of described decoating liquid is 40-70 ℃, and dipping time is 5-10min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210264913.5A CN103572306B (en) | 2012-07-30 | 2012-07-30 | For copper surface decoating liquid moving back nickel and preparation method thereof and the method for copper surface nickel of decorporating |
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| CN201210264913.5A CN103572306B (en) | 2012-07-30 | 2012-07-30 | For copper surface decoating liquid moving back nickel and preparation method thereof and the method for copper surface nickel of decorporating |
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| CN103572306B CN103572306B (en) | 2016-04-13 |
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Cited By (11)
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| CN104562055A (en) * | 2014-05-09 | 2015-04-29 | 扬州虹扬科技发展有限公司 | Novel nickel stripping treatment method |
| CN105239072A (en) * | 2015-11-11 | 2016-01-13 | 广州市太和电路板有限公司 | Electroplating hanger deplating solution and deplating method thereof |
| CN106011860A (en) * | 2016-07-21 | 2016-10-12 | 佛山市仁昌科技有限公司 | Technology for environment-friendly chemical deplating agent |
| CN106435616A (en) * | 2016-10-10 | 2017-02-22 | 深圳大学 | Deplating liquid of TiNC film and deplating process |
| CN106835142A (en) * | 2017-01-09 | 2017-06-13 | 苏州圣天迈电子科技有限公司 | Environmental protection stripping nickel passivator and its compound method and application method |
| CN108754498A (en) * | 2018-06-15 | 2018-11-06 | 西安微电子技术研究所 | A kind of method that cryochemistry nickel groove body deposited nickel layer takes off except solution and take off nickel layer |
| CN109957830A (en) * | 2017-12-25 | 2019-07-02 | 比亚迪股份有限公司 | A kind of strip method of positive pole oxidation film on aluminum alloy surface decoating liquid and positive pole oxidation film on aluminum alloy surface |
| WO2021168536A1 (en) * | 2020-02-28 | 2021-09-02 | Sixring Inc. | Sulfuric acid composition and uses thereof |
| WO2022178613A1 (en) * | 2021-02-25 | 2022-09-01 | Fluid Energy Group Ltd. | Modified sulfuric acid and uses thereof |
| WO2022178615A1 (en) * | 2021-02-25 | 2022-09-01 | Sixring Inc. | Modified sulfuric acid and uses thereof |
| US11760720B2 (en) | 2020-02-28 | 2023-09-19 | Sixring Inc. | Modified sulfuric acid and uses thereof |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104562055A (en) * | 2014-05-09 | 2015-04-29 | 扬州虹扬科技发展有限公司 | Novel nickel stripping treatment method |
| CN105239072A (en) * | 2015-11-11 | 2016-01-13 | 广州市太和电路板有限公司 | Electroplating hanger deplating solution and deplating method thereof |
| CN106011860A (en) * | 2016-07-21 | 2016-10-12 | 佛山市仁昌科技有限公司 | Technology for environment-friendly chemical deplating agent |
| CN106435616A (en) * | 2016-10-10 | 2017-02-22 | 深圳大学 | Deplating liquid of TiNC film and deplating process |
| CN106835142A (en) * | 2017-01-09 | 2017-06-13 | 苏州圣天迈电子科技有限公司 | Environmental protection stripping nickel passivator and its compound method and application method |
| CN109957830A (en) * | 2017-12-25 | 2019-07-02 | 比亚迪股份有限公司 | A kind of strip method of positive pole oxidation film on aluminum alloy surface decoating liquid and positive pole oxidation film on aluminum alloy surface |
| CN108754498A (en) * | 2018-06-15 | 2018-11-06 | 西安微电子技术研究所 | A kind of method that cryochemistry nickel groove body deposited nickel layer takes off except solution and take off nickel layer |
| US11760720B2 (en) | 2020-02-28 | 2023-09-19 | Sixring Inc. | Modified sulfuric acid and uses thereof |
| CN115461509A (en) * | 2020-02-28 | 2022-12-09 | 六环股份有限公司 | Sulfuric acid composition and use thereof |
| GB2608074A (en) * | 2020-02-28 | 2022-12-21 | Sixring Inc | Sulfuric acid compositions and uses thereof |
| WO2021168536A1 (en) * | 2020-02-28 | 2021-09-02 | Sixring Inc. | Sulfuric acid composition and uses thereof |
| US11846067B2 (en) | 2020-02-28 | 2023-12-19 | Sixring Inc. | Modified sulfuric acid and uses thereof |
| GB2608074B (en) * | 2020-02-28 | 2024-02-21 | Sixring Inc | Sulfuric acid composition and uses thereof |
| CN115461509B (en) * | 2020-02-28 | 2024-02-27 | 六环股份有限公司 | Sulfuric acid composition and use thereof |
| WO2022178613A1 (en) * | 2021-02-25 | 2022-09-01 | Fluid Energy Group Ltd. | Modified sulfuric acid and uses thereof |
| WO2022178615A1 (en) * | 2021-02-25 | 2022-09-01 | Sixring Inc. | Modified sulfuric acid and uses thereof |
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