CN104088007B - A kind of for the decoating liquid of Sintered NdFeB magnet surface nickel tungsten phosphorus galvanized coating stripping and the application of decoating liquid with withdrawal plating - Google Patents
A kind of for the decoating liquid of Sintered NdFeB magnet surface nickel tungsten phosphorus galvanized coating stripping and the application of decoating liquid with withdrawal plating Download PDFInfo
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- CN104088007B CN104088007B CN201410331058.4A CN201410331058A CN104088007B CN 104088007 B CN104088007 B CN 104088007B CN 201410331058 A CN201410331058 A CN 201410331058A CN 104088007 B CN104088007 B CN 104088007B
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Abstract
The invention discloses a kind of for the decoating liquid of Sintered NdFeB magnet surface nickel tungsten phosphorus galvanized coating stripping and the application of decoating liquid with withdrawal plating.Present invention discover that the decoating liquid that oxalic acid solution and phosphoric acid solution mix composition can be applied to the anode electrolysis strip of Sintered NdFeB magnet surface nickel tungsten phosphorus electrodeposited coating as electrolysis working solution；Withdrawal plating is in decoating liquid, surface is coated with the neodymium iron boron magnetic body of nickel tungsten phosphorus electrodeposited coating as anode, with inert electrode for negative electrode, carries out anode electrolysis strip；The decoating liquid utilizing the present invention carries out electrolytic deplating process, it is possible to directly utilize traditional electrolyte technique, it is not necessary to additional operations, and technique is simply ripe, and safety and environmental protection；Quickly, effectively by the stripping of nickel tungsten phosphorus electrodeposited coating totally, Sintered NdFeB magnet surface can not produced corrosion phenomenon, reaches to meet the plating substandard products recycling of Sintered NdFeB magnet, substantially realize the target that product zero is scrapped.
Description
Technical field
The present invention relates to a kind of for the decoating liquid of Sintered NdFeB magnet surface nickel tungsten phosphorus galvanized coating stripping and the application of decoating liquid with withdrawal plating, belong to field of metal material surface treatment.
Background technology
NdFeB magnetic material, as the latest result of rare earth permanent-magnetic material development, is referred to as " magnetic king " due to the magnetic property of its excellence.Simultaneously because china natural resources is enriched, relative low price, just all obtain a wide range of applications in fields such as electronics, machinery, traffic, communication, national defence, medical treatment, oil, environmental protection and agriculturals in recent years.But because its chemism is strong, the oxidizable corrosion in surface causes that magnet surface and structure change, and magnetic property sharply declines, and the most always causes that magnet efflorescence was lost efficacy.NiWP electrodeposited coating possesses the incomparable high rigidity of other coating, high heat stability, excellent corrosion resistance and anti-wear performance etc. and is widely applied on the base materials such as iron and steel, and 200810143741.X discloses the research of NdFeB magnet surface electroplated Ni WP alloy layer aspect.The weakness of the corrosion resistance difference of NdFeB magnet can be greatly improved by the method for electroplated Ni WP coating, but in the process of NdFeB magnet high-volume industry plating NiWP alloy layer, there will be some defective parts unavoidably, and NdFeB magnet is expensive, resource scarcity, in order to the substandard products of generation or waste product are recycled again, it is necessary to again electroplate after NiWP electrodeposited coating is stripped.At present, the decoating liquid major part removing NiWP electrodeposited coating is for steel substrate, when such decoating liquid is used for the NiWP electrodeposited coating on sintered NdFeB surface, the an ancient egg-shaped, holed wind instrument of sintered NdFeB matrix is hindered too big, the macro-size of magnet intrinsic changes too greatly, its recycling will be affected, even can not recycle.
Therefore, extensive use along with Sintered NdFeB magnet surface nickel tungsten phosphorus electrodeposited coating, it is badly in need of developing the decoating liquid of a kind of nickel tungsten phosphorus electrodeposited coating that can strip effectively quickly and evenly on Sintered NdFeB magnet, reach to meet the plating substandard products recycling of sintered NdFeB, substantially realize the target that the zero of product is scrapped.
Summary of the invention
It is an object of the invention to be in that to provide a kind of that Sintered NdFeB magnet corrosivity is little, the electrolytic stripping solution that electrolytic method is quick, effectively strip Sintered NdFeB magnet surface nickel tungsten phosphorus electrodeposited coating can be passed through.
Another object of the present invention is to be in that to provide the application on strip Sintered NdFeB magnet surface nickel tungsten phosphorus electrodeposited coating of a kind of described decoating liquid, has strip speed fast, effective, the feature that Sintered NdFeB magnet corrosion is little, is suitable for promoting the use of.
A further object of the invention is to be in that to provide a kind of technique adopting described decoating liquid strip sintered NdFeB surface nickel tungsten phosphorus electrodeposited coating, this technological operation is simple, can quickly, effectively strip sintered NdFeB surface nickel tungsten phosphorus electrodeposited coating, and do not corrode Sintered NdFeB magnet, reach to meet the requirement of the plating substandard products recycling of Sintered NdFeB magnet.
The invention provides a kind of decoating liquid for Sintered NdFeB magnet surface nickel tungsten phosphorus galvanized coating stripping, this decoating liquid is mixed by oxalic acid solution and phosphoric acid solution and forms；Wherein, the solute in every liter of water is composed of the following components: (COOH)210～100g；H3PO410～100mL.
The solute that preferred decoating liquid is in every liter of water is composed of the following components: (COOH)240～100g；H3PO440～80mL.
Described water can be tap water or distilled water.
Present invention also offers the application of described decoating liquid, this application is the anode electrolysis strip that described decoating liquid is applied to Sintered NdFeB magnet surface nickel tungsten phosphorus electrodeposited coating as electrolysis working solution.
Preferred application process is: in described electrolysis working solution, surface is coated with the neodymium iron boron magnetic body of nickel tungsten phosphorus electrodeposited coating as anode, using rustless steel or graphite or other metal insoluble in oxalic acid as negative electrode, carries out anode electrolysis strip.
It is preferred that application process in electrolysis temperature be 5～60 DEG C, anodic current density is 5～60A/dm2。
Present invention also offers the described decoating liquid technique for strip sintered NdFeB surface nickel tungsten phosphorus electrodeposited coating, this technique is first to prepare decoating liquid by proportioning, using the decoating liquid prepared as working solution, maintenance work liquid temp is 5～60 DEG C, the neodymium iron boron magnetic body being coated with nickel tungsten phosphorus electrodeposited coating with surface is anode, with rustless steel or graphite or other metal insoluble in oxalic acid for negative electrode, it is 5～60A/dm keeping anodic current density2When, carry out anode electrolysis strip, after electrolysis completes, anode is washed with water, obtain the neodymium iron boron magnetic body after strip.
Preferred electric current density is 15～35A/dm2。
The anode electrolysis strip method of the Sintered NdFeB magnet surface nickel tungsten phosphorus electrodeposited coating of the present invention, including step in detail below:
Step one: preparation decoating liquid
After adding volume required deionized water or clean tap water in a cell, then add required oxalic acid in the ratio of 10～100g/L；After oxalic acid is completely dissolved, then add phosphoric acid by 10～100mL/L；Stir, the decoating liquid obtained；
Step 2: strip
The temperature of decoating liquid is set to 5～60 DEG C, surface is coated with the neodymium iron boron magnetic body of nickel tungsten phosphorus electrodeposited coating as work package, oil removing, it is contained in after rinsing well with clear water on hanger, it is placed in the strip working solution of step one preparation, work package is as anode, and with rustless steel or graphite or other metal insoluble in oxalic acid for negative electrode, strip anodic current density is 5～60A/dm2, adopt Constant Direct Current electric current strip；
Step 3: clean
Neodymium iron boron magnetic body surface nickel tungsten phosphorus electrodeposited coating to be sintered moves back after only, takes out product, rinses the decoating liquid of product surface with clear water well, in order to coating again.
Beneficial effects of the present invention: the present invention adopts oxalic acid solution and the composite decoating liquid as Sintered NdFeB magnet surface nickel tungsten phosphorus electrodeposited coating of phosphoric acid solution first.The oxalic acid that the present invention adopts can react with nickel tungsten phosphorus electrodeposited coating, coating dissolves the metal ion discharged by phosphoric acid and oxalic acid complexation, and phosphoric acid runs into nickel ion and quickly generates nickel phosphate precipitation, greatly reduce nickel ion concentration in decoating liquid, oxalic acid and phosphoric acid cooperate, and play the effect of rapid solution coating；Having been surprisingly found that, Sintered NdFeB magnet has passive behavior in the oxalic acid solution and the composite decoating liquid of phosphoric acid solution of the present invention, effectively slows down or stops the decoating liquid corrosion to Sintered NdFeB magnet simultaneously.The decoating liquid utilizing the present invention carries out electrolytic deplating process, it is possible to directly utilize traditional electrolyte technique, it is not necessary to additional operations, and technique is simply ripe；Disposable can stripping speed fast effectively by clean for the stripping of nickel tungsten phosphorus electrodeposited coating, Sintered NdFeB magnet surface does not produce corrosion phenomenon, reaches to meet the plating substandard products recycling of Sintered NdFeB magnet, substantially realizes the target that product zero is scrapped.
Detailed description of the invention
Below in conjunction with specific embodiment, present disclosure is described further, but scope is not limited only to these examples.
Embodiment 1
The solvent of the decoating liquid of Sintered NdFeB magnet surface nickel tungsten phosphorus electrodeposited coating is deionized water, and the component of solute and content is: oxalic acid 60g/L；Phosphatase 24 0mL/L.
The decoating liquid prepared is heated to 30 DEG C and keeps constant temperature, then using underproof for coating Sintered NdFeB magnet as work package, oil removing, put into after rinsing well with clear water on hanger, put in above-mentioned decoating liquid, work package is as anode, negative electrode stainless steel substrates, and strip electric current density is 35A/dm2.After electrolytic removal nickel tungsten phosphorus electrodeposited coating, the nickel tungsten phosphorus electrodeposited coating described in work-piece surface is decorporated rapidly uniformly, takes out sample, rinse well with clear water, can again electroplate after strip is complete；After strip, Sintered NdFeB magnet apparent condition is as shown in table 1.
Embodiment 2
The solvent of the decoating liquid of Sintered NdFeB magnet surface nickel tungsten phosphorus electrodeposited coating is clean tap water, and the component of solute and content is: oxalic acid 100g/L；Phosphoric acid 50mL/L.
The decoating liquid prepared is heated to 25 DEG C and keeps constant temperature, then using underproof for coating Sintered NdFeB magnet as work package, oil removing, put into after rinsing well with clear water on hanger, put in above-mentioned decoating liquid, work package is as anode, negative electrode stainless steel substrates, and strip electric current density is 25A/dm2.After electrolytic removal nickel tungsten phosphorus electrodeposited coating, the nickel tungsten phosphorus electrodeposited coating described in work-piece surface is decorporated rapidly uniformly, takes out sample, rinse well with clear water, can again electroplate after strip is complete；After strip, Sintered NdFeB magnet apparent condition is as shown in table 1.
Embodiment 3
The solvent of the decoating liquid of Sintered NdFeB magnet surface nickel tungsten phosphorus electrodeposited coating is deionized water, and the component of solute and content is: oxalic acid 40g/L；Phosphoric acid 80mL/L.
The decoating liquid prepared is heated to 45 DEG C and keeps constant temperature, then using underproof for coating Sintered NdFeB magnet as work package, oil removing, put into after rinsing well with clear water on hanger, put in above-mentioned decoating liquid, work package is as anode, negative electrode stainless steel substrates, and strip electric current density is 15A/dm2.After electrolytic removal nickel tungsten phosphorus electrodeposited coating, the nickel tungsten phosphorus electrodeposited coating described in work-piece surface is decorporated rapidly uniformly, takes out sample, rinse well with clear water, can again electroplate after strip is complete；After strip, Sintered NdFeB magnet apparent condition is as shown in table 1.
Embodiment 4
The solvent of the decoating liquid of Sintered NdFeB magnet surface nickel tungsten phosphorus electrodeposited coating is clean tap water, and the component of solute and content is: oxalic acid 80g/L；Phosphoric acid 60mL/L.
The decoating liquid prepared is heated to 40 DEG C and keeps constant temperature, then using underproof for coating Sintered NdFeB magnet as work package, oil removing, put into after rinsing well with clear water on hanger, put in above-mentioned decoating liquid, work package is as anode, negative electrode stainless steel substrates, and strip electric current density is 20A/dm2.After electrolytic removal nickel tungsten phosphorus electrodeposited coating, the nickel tungsten phosphorus electrodeposited coating described in work-piece surface is decorporated rapidly uniformly, takes out sample, rinse well with clear water, can again electroplate after strip is complete；After strip, Sintered NdFeB magnet apparent condition is as shown in table 1.
Comparative example 1
The solvent of the decoating liquid of Sintered NdFeB magnet surface nickel tungsten phosphorus electrodeposited coating is deionized water, adopts the withdrawal plating of nickel tungsten phosphorus electrodeposited coating on conventional steel substrate, and in its decoating liquid, the component of solute and content are: sodium nitrate 400g/L.
The decoating liquid prepared is heated to 30 DEG C and keeps constant temperature, then using underproof for coating Sintered NdFeB magnet as work package, oil removing, put into after rinsing well with clear water on hanger, put in above-mentioned decoating liquid, work package is as anode, negative electrode stainless steel substrates, and strip electric current density is 20A/dm2.After electrolytic removal nickel tungsten phosphorus electrodeposited coating, the nickel tungsten phosphorus electrodeposited coating described in work-piece surface is decorporated rapidly uniformly, takes out sample, rinse well with clear water after strip is complete, observes and finds that Sintered NdFeB magnet surface corrosion is serious, and matrix macro-size changes greatly.
Sintered NdFeB magnet apparent condition after table 1 strip
| Surface quality | |
| Embodiment 1 | Surfacing is smooth, it does not have burn into an ancient egg-shaped, holed wind instrument is hindered |
| Embodiment 2 | Surfacing is smooth, it does not have burn into an ancient egg-shaped, holed wind instrument is hindered |
| Embodiment 3 | Surfacing is smooth, it does not have burn into an ancient egg-shaped, holed wind instrument is hindered |
| Embodiment 4 | Surfacing is smooth, it does not have burn into an ancient egg-shaped, holed wind instrument is hindered |
| Comparative example 1 | Matrix has obvious corrosion depth, affects the macro-size of base material |
As can be seen from Table 1, by the strip method of the present invention, Sintered NdFeB magnet surface nickel tungsten phosphorus electrodeposited coating being carried out strip, Sintered NdFeB magnet surfacing is smooth, it does not have be corroded, do not affect follow-up magnet to return to coating bath and electroplate, and the macro-size change of magnet is little.And with the strip that Sintered NdFeB magnet surface nickel tungsten phosphorus electrodeposited coating is carried out by the method for comparative example, there is obvious corrosion on Sintered NdFeB magnet surface, and having certain corrosion depth, it is necessary to degree of depth sanding and polishing can be electroplated again, and the macro-size of base material is altered a great deal.
Claims (6)
1. the application for the decoating liquid of Sintered NdFeB magnet surface nickel tungsten phosphorus galvanized coating stripping, it is characterised in that described decoating liquid is applied to the anode electrolysis strip of Sintered NdFeB magnet surface nickel tungsten phosphorus electrodeposited coating as electrolysis working solution；
Described decoating liquid is mixed by oxalic acid solution and phosphoric acid solution and forms；Wherein, the solute in every liter of water is composed of the following components: (COOH)210～100g；H3PO410～100mL.
2. apply as claimed in claim 1, it is characterised in that the solute in every liter of water is composed of the following components: (COOH)240～100g；H3PO440～80mL.
3. apply as claimed in claim 2, it is characterised in that in described electrolysis working solution, surface is coated with the neodymium iron boron magnetic body of nickel tungsten phosphorus electrodeposited coating as anode, using rustless steel or graphite or other metal insoluble in oxalic acid as negative electrode, carry out anode electrolysis strip.
4. applying as claimed in claim 3, it is characterised in that electrolysis temperature is 5～60 DEG C, anodic current density is 5～60A/dm2。
5. the method that a decoating liquid is used for strip sintered NdFeB surface nickel tungsten phosphorus electrodeposited coating, it is characterized in that, first by proportioning preparation decoating liquid, using the decoating liquid prepared as working solution, maintenance work liquid temp is 5～60 DEG C, the neodymium iron boron magnetic body being coated with nickel tungsten phosphorus electrodeposited coating with surface is anode, with rustless steel or graphite or other metal insoluble in oxalic acid for negative electrode, is 5～60A/dm keeping anodic current density2When, carry out anode electrolysis strip, after electrolysis completes, anode is washed with water, obtain the neodymium iron boron magnetic body after strip；Described decoating liquid is mixed by oxalic acid solution and phosphoric acid solution and forms；Wherein, the solute in every liter of water is composed of the following components: (COOH)210～100g；H3PO410～100mL.
6. method as claimed in claim 5, it is characterised in that anodic current density maintains 15～35A/dm2。
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| CN201410331058.4A CN104088007B (en) | 2014-07-11 | 2014-07-11 | A kind of for the decoating liquid of Sintered NdFeB magnet surface nickel tungsten phosphorus galvanized coating stripping and the application of decoating liquid with withdrawal plating |
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| CN201410331058.4A CN104088007B (en) | 2014-07-11 | 2014-07-11 | A kind of for the decoating liquid of Sintered NdFeB magnet surface nickel tungsten phosphorus galvanized coating stripping and the application of decoating liquid with withdrawal plating |
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| CN104088007B true CN104088007B (en) | 2016-07-20 |
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| GB336532A (en) * | 1929-03-06 | 1930-10-16 | Ternstedt Mfg Co | Improved method and means for stripping chromium plating |
| US3619390A (en) * | 1969-02-21 | 1971-11-09 | Horst Dillenberg | Aqueous electrolytic stripping bath to remove metal coatings from bases of steel |
| JPH0741965A (en) * | 1993-07-23 | 1995-02-10 | Asahi Glass Co Ltd | Method for dissolving metallic film |
| CN102644080A (en) * | 2012-04-28 | 2012-08-22 | 杭州广荣科技有限公司 | Stripping liquid for sintering neodymium iron boron magnet chemical nickel plating layers |
| CN102787321A (en) * | 2012-07-30 | 2012-11-21 | 牛凯 | Deplating liquid for NiCuNi plating on surface of sintered NdFeB and deplating process thereof |
| CN103757633A (en) * | 2014-01-15 | 2014-04-30 | 成都青元表面技术有限责任公司 | Magnesium alloy nickel coating stripping method |
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2014
- 2014-07-11 CN CN201410331058.4A patent/CN104088007B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB336532A (en) * | 1929-03-06 | 1930-10-16 | Ternstedt Mfg Co | Improved method and means for stripping chromium plating |
| US3619390A (en) * | 1969-02-21 | 1971-11-09 | Horst Dillenberg | Aqueous electrolytic stripping bath to remove metal coatings from bases of steel |
| JPH0741965A (en) * | 1993-07-23 | 1995-02-10 | Asahi Glass Co Ltd | Method for dissolving metallic film |
| CN102644080A (en) * | 2012-04-28 | 2012-08-22 | 杭州广荣科技有限公司 | Stripping liquid for sintering neodymium iron boron magnet chemical nickel plating layers |
| CN102787321A (en) * | 2012-07-30 | 2012-11-21 | 牛凯 | Deplating liquid for NiCuNi plating on surface of sintered NdFeB and deplating process thereof |
| CN103757633A (en) * | 2014-01-15 | 2014-04-30 | 成都青元表面技术有限责任公司 | Magnesium alloy nickel coating stripping method |
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