CN103572306B - For copper surface decoating liquid moving back nickel and preparation method thereof and the method for copper surface nickel of decorporating - Google Patents
For copper surface decoating liquid moving back nickel and preparation method thereof and the method for copper surface nickel of decorporating Download PDFInfo
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- CN103572306B CN103572306B CN201210264913.5A CN201210264913A CN103572306B CN 103572306 B CN103572306 B CN 103572306B CN 201210264913 A CN201210264913 A CN 201210264913A CN 103572306 B CN103572306 B CN 103572306B
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Abstract
The invention provides a kind of decoating liquid moving back nickel for copper surface, the aqueous solution containing following component in described decoating liquid: sulfuric acid 100-200g/L; Hydrogen peroxide 50-200g/L; Quadrol 90-270g/L; Halfcystine 5-50g/L; Thionamic acid 1-10g/L.Present invention also offers the preparation method of this decoating liquid and adopt this decoating liquid to decorporate the method for copper surface nickel.Adopt decoating liquid provided by the invention at room temperature can treat strip workpiece to process; volatile irritating smell gas is produced hardly in strip process; very environmental protection, can not affect layers of copper quality, the quality of thickness coating and the bonding force between layers of copper and subsequent plating layer simultaneously.
Description
Technical field
The invention belongs to chemical strip technical field, particularly relate to a kind of for copper surface decoating liquid moving back nickel and preparation method thereof and a kind of method for copper surface nickel of decorporating.
Background technology
Often need metallizing nickel dam on metallic copper anticorrosion, antirust to play in modern electroplating technology, or on metallic copper, plate other metal transfer coating.Because nickel layer easily occurs quality problems in copper plating nickel on surface process, after therefore needing strip nickel dam, re-start Nickel Plating Treatment again.About coating withdrawal plating, the method for chemistry or electrochemistry stripping generally can be adopted.Electrochemical method stripping liquid composition is simple, faint to base material corrosion, be conducive to environment protection to some metal recoverable, but needs to provide power supply and strip groove, and sometimes need special hanger, this is disadvantageous for the workshop of not producing in enormous quantities.In addition, owing to being generally complex geometric shapes in waste material, be always difficult to ensure that low current density and high current density place coating are all made part not be corroded by dissolving stripping in electrolytic removal process, the application that electrochemistry is stripped 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 layers of copper, causes product rejection.In current chemical strip method, conventional strip agent is the mixed system of potassium sulfocyanate and m-nitrobenzene sodium sulfonate, can form at copper surface the film that one deck is difficult to wash off, bonding force when affecting follow-up metal lining again between coating and copper after on the one hand adopting this strip agent to carry out strip process; 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 generation harmful property volatility irritant gas of the strip agent existence of chemical strip method use in prior art, affect the quality of layers of copper and subsequent plating layer and the technical problem of bonding force simultaneously.
The invention provides a kind of decoating liquid moving back nickel for copper surface, the aqueous solution containing following component in described decoating liquid:
Sulfuric acid 100-200g/L;
Hydrogen peroxide 50-200g/L;
Quadrol 90-270g/L;
Halfcystine 5-50g/L;
Thionamic acid 1-10g/L.
Present invention also offers the preparation method of described decoating liquid, comprise 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 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 oxygenant of compound system as metallic nickel of sulfuric acid and hydrogen peroxide; exempt to be corroded by quadrol and halfcystine coordinating protection metallic copper simultaneously; and dissolved the speed of moving back nickel by the agent of thionamic acid controlled oxidization, thus the metallic nickel on copper surface thoroughly can be removed under the prerequisite protecting copper not to be corroded.Adopt decoating liquid provided by the invention at room temperature can treat strip workpiece to process; and in strip process, produce volatile irritating smell gas hardly; very environmental protection, can not affect layers of copper quality, the quality of thickness coating and the bonding force between layers of copper and subsequent plating layer simultaneously.
Embodiment
The invention provides a kind of decoating liquid moving back nickel for copper surface, the aqueous solution containing following component in described decoating liquid:
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 oxygenant of compound system as metallic nickel of sulfuric acid and hydrogen peroxide; exempt to be corroded by quadrol and halfcystine coordinating protection metallic copper simultaneously; and dissolved the speed of moving back nickel by the agent of thionamic acid controlled oxidization, thus the metallic nickel on copper surface thoroughly can be removed under the prerequisite protecting copper not to be corroded.
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.
Present invention also offers the preparation method of described decoating liquid, comprise 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 hydrogen peroxide, quadrol and halfcystine successively, obtain mixed system; Be dissolved in the water thionamic acid formation sulfamic acid solution, then mixed with mixed system by sulfamic acid solution, obtains described decoating liquid.
Finally, the invention provides a kind of method for 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 ensureing 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 has nickel, such as, in the present invention, described in treat strip workpiece to be surface sequentially laminated with the plastics part of metallic copper and metallic nickel, surface be laminated with sequentially laminated with the ceramic workpiece of metallic copper and metallic nickel or surface the metallic copper workpiece of metallic nickel.
Adopt decoating liquid provided by the invention at room temperature can treat strip workpiece to process, and in strip process, volatility is few, very environmental protection, layers of copper quality, the quality of thickness coating and the bonding force between layers of copper and subsequent plating layer can not be affected simultaneously.When adopting decoating liquid provided by the invention to carry out strip process to layers of copper surface metal nickel dam, the temperature of decoating liquid and strip immersion treatment time suitably can be selected according to the concrete thickness of nickel dam.Such as, when described metallic nickel be thickness is the chemical Ni-plating layer of 1-10 micron, the temperature of described decoating liquid is 40-70 DEG C, and dipping time is 5-10min.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, 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, be not intended to limit the present invention.
Embodiment 1
First sulfuric acid is mixed with the aqueous solution by following formula, thionamic acid is mixed with the aqueous solution; Then in aqueous sulfuric acid, add hydrogen peroxide, quadrol and halfcystine successively, obtain mixed system; Then mixed with mixed system by aqueous sulfamic acid, 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
First sulfuric acid is mixed with the aqueous solution by following formula, thionamic acid is mixed with the aqueous solution; Then in aqueous sulfuric acid, add hydrogen peroxide, quadrol and halfcystine successively, obtain mixed system; Then mixed with mixed system by aqueous sulfamic acid, 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
First sulfuric acid is mixed with the aqueous solution by following formula, thionamic acid is mixed with the aqueous solution; Then in aqueous sulfuric acid, add hydrogen peroxide, quadrol and halfcystine successively, obtain mixed system; Then mixed with mixed system by aqueous sulfamic acid, 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
First sulfuric acid is mixed with the aqueous solution by following formula, thionamic acid is mixed with the aqueous solution; Then in aqueous sulfuric acid, add hydrogen peroxide, quadrol and halfcystine successively, obtain mixed system; Then mixed with mixed system by aqueous sulfamic acid, 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
Sulfuric acid, hydrogen peroxide, halfcystine, thionamic acid are dissolved in the water according to the following ratio: sulfuric acid 150g/L, hydrogen peroxide 100g/L, halfcystine 7g/L, thionamic acid 5g/L, obtain the decoating liquid DS1 of the present embodiment.
Comparative example 2
Sulfuric acid, hydrogen peroxide, quadrol, thionamic acid are dissolved in the water according to the following ratio: sulfuric acid 150g/L, hydrogen peroxide 100g/L, quadrol 180g/L, thionamic acid 5g/L, obtain the decoating liquid DS2 of the present embodiment.
Comparative example 3
Sulfuric acid, hydrogen peroxide are dissolved in the water according to the following ratio: sulfuric acid 150g/L, hydrogen peroxide 100g/L obtains the decoating liquid DS3 of the present embodiment.
Comparative example 1
M-nitrobenzene sodium sulfonate, potassium sulfocyanate are dissolved in the water according to the following ratio: 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 chemical Ni-plating layer of 3 microns (the surperficial nickel dam to be thickness be) surface being coated with successively layers of copper and nickel dam impregnated in decoating liquid S1-S4 and DS1-DS4 respectively, constantly stirs decoating liquid in steeping process; Estimate and take out workpiece after nickel dam is removed by complete strip, record the time of each workpiece surface strip nickel dam.Record the smell size of the irritant gas produced in strip process, and after observing strip, whether workpiece surface metallic copper is corroded phenomenon simultaneously.
Test result is as shown in table 1.
Table 1
。
As can be seen from the test result of upper table 1, adopt the decoating liquid that passes through of the present invention the metallic nickel on copper surface thoroughly can be stripped, and not attack copper surfaces, produce volatile irritating smell gas hardly or produce less, very environmental protection in strip process simultaneously.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. move back a decoating liquid for nickel for copper surface, it is characterized in that, the aqueous solution containing following component in described decoating liquid:
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 hydrogen peroxide, quadrol and halfcystine successively, obtains mixed system; Be dissolved in the water thionamic acid formation sulfamic acid solution, then mixed with mixed system by sulfamic acid solution, obtains described decoating liquid.
5. for a method for copper surface nickel of decorporating, it is characterized in that, comprise and will treat in the decoating liquid that strip workpiece impregnated in 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 impregnated in until strip workpiece the step stirring decoating liquid after in decoating liquid.
7. method according to claim 5, it is characterized in that, described in treat strip workpiece to be surface sequentially laminated with the plastics part of metallic copper and metallic nickel, surface be laminated with sequentially laminated with the ceramic workpiece of metallic copper and metallic nickel or surface the metallic copper workpiece of metallic nickel.
8. the method according to claim 5 or 7, the chemical Ni-plating layer of described metallic nickel to be thickness be 1-10 micron; The temperature of described decoating liquid is 40-70 DEG C, and dipping time is 5-10min.
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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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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN106435616B (en) * | 2016-10-10 | 2018-09-07 | 深圳大学 | A kind of decoating liquid and withdrawal plating of TiNC films |
| 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 |
| CN109957830B (en) * | 2017-12-25 | 2021-02-23 | 比亚迪股份有限公司 | Deplating solution and deplating method for anodic oxide film on surface of aluminum alloy |
| 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 |
| CA3074194A1 (en) | 2020-02-28 | 2021-08-28 | Fluid Energy Group Ltd. | Modified sulfuric acid and uses thereof |
| CA3074199A1 (en) | 2020-02-28 | 2021-08-28 | Fluid Energy Group Ltd. | Modified sulfuric acid and uses thereof |
| CA3110360A1 (en) * | 2021-02-25 | 2022-08-25 | Sixring Inc. | Modified sulfuric acid and uses thereof |
| CA3110391A1 (en) * | 2021-02-25 | 2022-08-25 | Fluid Energy Group Ltd | Modified sulfuric acid and uses thereof |
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