CN104630852A - Rare earth permanent magnet with multilayer composite electroplated coating and composite electroplating method thereof - Google Patents

Rare earth permanent magnet with multilayer composite electroplated coating and composite electroplating method thereof Download PDF

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CN104630852A
CN104630852A CN201310560338.8A CN201310560338A CN104630852A CN 104630852 A CN104630852 A CN 104630852A CN 201310560338 A CN201310560338 A CN 201310560338A CN 104630852 A CN104630852 A CN 104630852A
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layer
nickel
coating
electroplate liquid
grams per
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CN201310560338.8A
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CN104630852B (en
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白晓刚
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天津三环乐喜新材料有限公司
北京中科三环高技术股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • H—ELECTRICITY
    • H01—BASIC ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0572—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes with a protective layer
    • H—ELECTRICITY
    • H01—BASIC ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/026—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets protecting methods against environmental influences, e.g. oxygen, by surface treatment
    • H—ELECTRICITY
    • H01—BASIC ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F7/00—Magnets
    • H01F7/02—Permanent magnets [PM]

Abstract

The invention provides a rare earth permanent magnet with a multilayer composite electroplated coating and a composite electroplating method thereof. The rare earth permanent magnet includes a rare earth permanent magnet body, a first layer of nickel coating, a second layer of copper coating, a third layer of nickel coating and a fourth layer. An electroplating solution includes: 40-60g/L stannous pyrophosphate, 30-45g/L nickel chloride, 250-320g/L potassium pyrophosphate, and 20g/L glycine. The composite electroplated coating not only can play an anti-corrosion role of conventional electroplated nickel, but also has certain protection effect on the eyes of inspectors, and the uniform appearance and black and shiny color can reach certain decorative effect.

Description

There is rare-earth permanent magnet and the composite electric plating method thereof of MULTILAYER COMPOSITE electrolytic coating

Technical field

The present invention relates to the field of surface treatment of material, especially relate to the rare-earth permanent magnet and composite electric plating method thereof with MULTILAYER COMPOSITE electrolytic coating.

Background technology

The application and development of neodymium iron boron (NdFeB) permanent magnet material is very rapid in recent years, and the protection success or not of Nd-Fe-Bo permanent magnet material is related to one of gordian technique that can material apply.This material is mainly prepared from by powder metallurgical technique by elements such as rare earth metal neodymium Nd, iron and boron.As magneticsubstance the strongest at present, be widely used in all fields such as electroplating device, machinery, medical treatment, automobile, application prospect is very wide.

The prerequisite of Nd-Fe-Bo permanent magnet material application first to resolve the Anticorrosion of Nd-Fe-Bo permanent magnet material.As the porous material that a kind of powder metallurgical technique is prepared from, because of rich neodymium phase wherein, neodymium iron boron principal phase and border are easy to form intergranular corrosion mutually.Rear earth element nd in neodymium iron boron powder metallurgy, character is active, the corrosion resisting property of whole Nd-Fe-B alloys is made to become very poor, very easily corrosion in damp and hot environment, because corrosion failure causes decline or the damage of magnetic property, have a strong impact on the work-ing life of Nd-Fe-B permanent magnet, reduce stability and the reliability of product.The magnetic property of Nd-Fe-Bo permanent magnet material and its weave construction have very large relation.The principal phase of Nd-Fe-B permanent magnet is the main source of magnet magnetic property.Maximum to coercive force contribution is rich neodymium phase.To there is huge change in the magnetic property of material after corrosion occurs Nd-Fe-Bo permanent magnet material.Therefore, the Anticorrosion of Nd-Fe-Bo permanent magnet material is the subject matter that Nd-Fe-Bo permanent magnet material needs to solve always.

The anti-corrosion method of current Nd-Fe-Bo permanent magnet material has a lot.Wherein there are electronickelling, electro-galvanizing (CN1421547A, CN1056133A), shooting of multi-layer nickel electroplating (CN102568732CN200910244404), copper facing (CN1514889A), the multiple methods such as phosphatization (CN101022051), electrocoating paint.

At present, Nd-Fe-B permanent magnet is more applied in consumer electronics product, and the general volume of consumer electronics product is little, adopts the method for manual detection to test to bad product.General Nd-Fe-B permanent magnet adopts the method surface-brightening of electronickelling, and inspector's inspection for a long time can cause detrimentally affect to eyes etc.

Summary of the invention

In order to overcome above-mentioned prior art Problems existing; the invention provides a kind of rare-earth permanent magnet with MULTILAYER COMPOSITE electrolytic coating; and composite electric plating method is carried out on this permanent magnet; this composite galvanized coating can not only play the anticorrosion ability of conventional electronickelling; and have certain protection for the eyes of inspector; and appearance uniform, color and luster is shiny black certain decorative effect.

According to an aspect of the present invention, the invention provides a kind of rare-earth permanent magnet with MULTILAYER COMPOSITE electrolytic coating, described rare-earth permanent magnet comprises rare-earth permanent magnet, the first layer nickel coating, second layer copper coating, third layer nickel coating, the 4th layer of gun barrel RIFLE tin nickel dam; Wherein, coating total thickness is not more than 30 μm, thickness≤5 μm of the first layer, thickness≤10 μm of the described second layer, thickness≤20 μm of third layer; The electroplate liquid of described 4th layer of rifle look tin-nickel coating comprises: stannous pyrophosphate 40 ~ 60 grams per liter, nickelous chloride 30 ~ 45 grams per liter, potassium pyrophosphate 250 ~ 320 grams per liter, glycine 20 grams per liter.

Preferably, the electroplating time of described 4th layer of rifle look tin-nickel coating is 1 ~ 5 point, and the pH of described electroplate liquid is 7.0 ~ 8.5.

Preferably, described the first layer nickel coating adopts the formula of watt nickel to obtain, and wherein, the pH value range of described electroplate liquid is 3.5 ~ 5.5, and temperature range is 35 ~ 60 DEG C, and Ni 2+concentration range is 1.0 ~ 2.0mol/L; The electroplate liquid of described second layer copper coating adopts the formula of cupric pyrophosphate plating solution to obtain, and wherein, the pH value range of described electroplate liquid is 7.0 ~ 9.5, and temperature range is 35 ~ 60 DEG C, and Cu 2+concentration range is 0.3 ~ 0.6mol/L; The electroplate liquid of described third layer nickel coating adopts commercially available brightening agent to be mixed with semi-bright nickel electroplate liquid and/or bright nickel electroplate liquid, and wherein, the pH value range of described semi-bright nickel electroplate liquid is 4.0, and temperature range is 60 DEG C, and Ni 2+concentration range is 1.5 ~ 2.0mol/L; The pH value range of described bright nickel electroplate liquid is 3.5 ~ 4.5, and temperature range is 60 DEG C, and Ni 2+concentration range is 2.0mol/L.

According to a further aspect in the invention, present invention also offers one and carry out composite electric plating method on rare-earth permanent magnet, described method comprises the steps: that (1) adopts mechanical vibration, barreling chamfering carries out routine polishing to Nd-Fe-Bo permanent magnet material; (2) degreasing degreasing: add alkaline degreaser and carry out conventional degreasing degreasing; (3) acid pickling and rust removing: add acidic solution again and carry out conventional acid pickling and rust removing; (4) four layers of composite plating: first plate the first layer nickel coating, then plate second layer copper coating, second layer copper coating plates third layer nickel coating and (5) finally plate the 4th layer of rifle look tin-nickel coating again.Wherein, coating total thickness is not more than 30 μm, and the electroplate liquid of described 4th layer of rifle look tin-nickel coating comprises: stannous pyrophosphate 40 ~ 60 grams per liter, nickelous chloride 30 ~ 45 grams per liter potassium pyrophosphate, 250 ~ 320 grams per liters, glycine 20 grams per liter.

Preferably, the electroplating time of described 4th layer of nickel coating is 1 ~ 5 point, and the pH of described electroplate liquid is 7.0 ~ 8.5.

Preferably, described the first layer nickel coating adopts the formula of watt nickel to obtain, and wherein, the pH value range of described electroplate liquid is 3.5 ~ 5.5, and temperature range is 35 ~ 60 DEG C, and Ni 2+concentration range is 1.0 ~ 2.0mol/L; The electroplate liquid of described second layer copper coating adopts the formula of cupric pyrophosphate plating solution to obtain, and wherein, the pH value range of described electroplate liquid is 7.0 ~ 9.5, and temperature range is 35 ~ 60 DEG C, and Cu 2+concentration range is 0.3 ~ 0.6mol/L; The electroplate liquid of described third layer nickel coating adopts commercially available brightening agent to be mixed with semi-bright nickel electroplate liquid and/or bright nickel electroplate liquid, and wherein, the pH value range of described semi-bright nickel electroplate liquid is 4.0, and temperature range is 60 DEG C, and Ni 2+concentration range is 1.5 ~ 2.0mol/L; The pH value range of described bright nickel electroplate liquid is 3.5 ~ 4.5, and temperature range is 60 DEG C, and Ni 2+concentration range is 2.0mol/L.

A kind of MULTILAYER COMPOSITE plating provided by the invention improves the method for rare-earth permanent magnet corrosion resistance of surface; compared with prior art; this composite galvanized coating can not only play the anticorrosion ability of conventional electronickelling; and have certain protection for the eyes of inspector; and appearance uniform, color and luster is shiny black certain decorative effect.After this process, plating bonding force is identical with electronickelling, and antiseptic power is identical with shooting of multi-layer nickel electroplating.Salt-fog test reaches 48 hours.The present invention has filled up the blank of domestic neodymium-iron-boron permanent magnetic material surface process.

Accompanying drawing explanation

Fig. 1 is the coating composition adopting Electronic Speculum to show outermost layer rifle color coating energy spectrogram.

Embodiment

Below with reference to embodiment, the present invention will be further described, and embodiments of the invention are only for illustration of technical scheme of the present invention, and non-limiting the present invention.

Embodiment 1

Will sintered Nd-Fe-B permanent magnetic material 2.3 kilograms of elder generations in vibrating ball mill, polish 2 hours.Through sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after sodium hydroxide 10g/ rises degreasing degreasing, pickling removing oxide on surface in 1% nitric acid, washing, plating the first layer nickel coating, electronickelling is Common platings watt nickel, plating solution formula is as follows: single nickel salt 275 grams per liter, nickelous chloride 30 grams per liter, boric acid 40 grams per liter, pH3.5, temperature 60 C, nickel concentration is 2.0mol/ liter, electronickelling thickness 5 microns.

With after washing, adopt electroplating copper pyrophosphate plating second layer copper coating, cupric pyrophosphate formula is as follows: cupric pyrophosphate 90 grams per liter, potassium pyrophosphate 320 grams per liter, and copper concentration is 0.6mol/ liter, pH7.0, temperature 55 DEG C, thickness of coating 7 microns.

Then, adopt bright nickel electroplate liquid plating third layer nickel coating, bright nickel electroplate liquid formulation following single nickel salt 275 grams per liter, nickelous chloride 30 grams per liter, boric acid 40 grams per liter, pH3.5, temperature 60 C, nickel concentration is 2.0mol/ liter, interpolation Atotech light external additive W-100A0.5 milliliter/liter, 100-B3 milliliter/liter, Y191.5 milliliter/liter: electroplating bright nickel coating thickness 10 microns.

After washing, after third layer nickel coating plates the 4th layer of rifle color coating again, the electroplate liquid of described 4th layer of nickel rifle color coating comprises: stannous pyrophosphate 40 grams per liter, nickelous chloride 30 grams per liter, potassium pyrophosphate 250 grams per liter, glycine 20 grams per liter.Electroplate 1 minute pH=8.5, temperature 20 DEG C, coating binding force is good, and cross cut test is qualified, and Corrosion Protection is see table 1.The coating composition of outermost layer rifle color coating energy spectrogram display refers to Fig. 1.

Embodiment 2

Will sintered Nd-Fe-B permanent magnetic material 2.3 kilograms of elder generations in vibrating ball mill, polish 2 hours.Through sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after sodium hydroxide 10g/ rises degreasing degreasing, pickling removing oxide on surface in 1% nitric acid, washing, plating the first layer nickel coating, electronickelling is Common platings watt nickel, plating solution formula is as follows: single nickel salt 150 grams per liter, nickelous chloride 20 grams per liter, boric acid 40 grams per liter, pH4.5, temperature 35 DEG C, nickel concentration is 1.0mol/ liter, electronickelling thickness 3 microns.

With after washing, adopt electroplating copper pyrophosphate plating second layer copper coating, cupric pyrophosphate formula is as follows: cupric pyrophosphate 45 grams per liter, potassium pyrophosphate 240 grams per liter, and copper concentration is 0.3mol/ liter, pH9.5, temperature 60 C, thickness of coating 10 microns.

Then, adopt bright nickel electroplate liquid plating third layer nickel coating, bright nickel electroplate liquid formulation following single nickel salt 275 grams per liter, nickelous chloride 30 grams per liter, boric acid 40 grams per liter, pH3.5, temperature 60 C, nickel concentration is 2.0mol/ liter, interpolation Atotech light external additive W-100A0.5 milliliter/liter, 100-B3 milliliter/liter, Y191.5 milliliter/liter: electroplating bright nickel coating thickness 15 microns.

After washing, after third layer nickel coating plates the 4th layer of rifle color coating again, the electroplate liquid of described 4th layer of nickel rifle color coating comprises: stannous pyrophosphate 60 grams per liter, nickelous chloride 45 grams per liter, potassium pyrophosphate 320 grams per liter, glycine 20 grams per liter.PH=8.5 temperature 25 DEG C plating 3 minutes coating binding forces are good, and cross cut test is qualified, and Corrosion Protection is see table 1.

Embodiment 3

Will sintered Nd-Fe-B permanent magnetic material 2.3 kilograms of elder generations in vibrating ball mill, polish 2 hours.Through sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after sodium hydroxide 10g/ rises degreasing degreasing, pickling removing oxide on surface in 1% nitric acid, washing, plating the first layer nickel coating, electronickelling is Common platings watt nickel, plating solution formula is as follows: single nickel salt 200 grams per liter, nickelous chloride 30 grams per liter, boric acid 40 grams per liter, pH3.5, temperature 55 DEG C, nickel concentration is 1.5mol/ liter, electronickelling thickness 4 microns.

With after washing, adopt electroplating copper pyrophosphate plating second layer copper coating, cupric pyrophosphate formula is as follows: cupric pyrophosphate 75 grams per liter, potassium pyrophosphate 280 grams per liter, and copper concentration is 0.5mol/ liter, pH8.0, temperature 55 DEG C, thickness of coating 10 microns.

Then, first adopt semi-bright nickel electroplate liquid plating third layer nickel coating, semi-bright nickel electroplate liquid formulation following single nickel salt 275 grams per liter, nickelous chloride 30 grams per liter, boric acid 40 grams per liter, pH4.0, temperature 60 C, nickel concentration is 2.0mol/ liter, interpolation Atotech half brightener M-9010.5 milliliter/liter, M9020.5 milliliter/liter, NP-A1.5 milliliter/.Bright nickel electroplate liquid is adopted to electroplate third layer nickel coating again, bright nickel electroplate liquid formulation following single nickel salt 275 grams per liter, nickelous chloride 30 grams per liter, boric acid 40 grams per liter, pH3.5, temperature 60 C, nickel concentration is 2.0mol/ liter, interpolation Atotech light external additive W-100A0.5 milliliter/liter, 100-B3 milliliter/liter, Y191.5 milliliter/liter: plating semi-bright nickel and bright nickel coat-thickness 15 microns.

After washing, after third layer nickel coating plates the 4th layer of rifle color coating again, the electroplate liquid of described 4th layer of nickel rifle color coating comprises: stannous pyrophosphate 50 grams per liter, nickelous chloride 45 grams per liter, potassium pyrophosphate 280 grams per liter, glycine 20 grams per liter.PH=8.6, temperature 24 DEG C, electroplate 2 minutes coating binding forces good, cross cut test is qualified, and Corrosion Protection is see table 1.

Embodiment 4

Will sintered Nd-Fe-B permanent magnetic material 2.3 kilograms of elder generations in vibrating ball mill, polish 2 hours.Through sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after sodium hydroxide 10g/ rises degreasing degreasing, pickling removing oxide on surface in 1% nitric acid, washing, plating the first layer nickel coating, electronickelling is Common platings watt nickel, plating solution formula is as follows: single nickel salt 275 grams per liter, nickelous chloride 30 grams per liter, boric acid 40 grams per liter, pH3.5, temperature 60 C, nickel concentration is 2.0mol/ liter, electronickelling thickness 5 microns.

With after washing, adopt electroplating copper pyrophosphate plating second layer copper coating, cupric pyrophosphate formula is as follows: cupric pyrophosphate 75 grams per liter, potassium pyrophosphate 280 grams per liter, and copper concentration is 0.5mol/ liter, pH8.5, temperature 55 DEG C, thickness of coating 9 microns.

Then, first adopt semi-bright nickel electroplate liquid plating third layer nickel coating, semi-bright nickel electroplate liquid formulation following single nickel salt 200 grams per liter, nickelous chloride 30 grams per liter, boric acid 40 grams per liter, pH4.0, temperature 60 C, nickel concentration is 1.5mol/ liter, interpolation Atotech half brightener M-9010.5 milliliter/liter, M9020.5 milliliter/liter, NP-A1.5 milliliter/liter.Bright nickel electroplate liquid is adopted to electroplate again, bright nickel electroplate liquid formulation following single nickel salt 275 grams per liter, nickelous chloride 30 grams per liter, boric acid 40 grams per liter, pH3.5, temperature 60 C, nickel concentration is 2.0mol/ liter, interpolation Atotech light external additive W-100A0.5 milliliter/liter, 100-B3 milliliter/liter, Y191.5 milliliter/liter: plating semi-bright nickel and bright nickel coat-thickness 12 microns.

After washing, after third layer nickel coating plates the 4th layer of rifle color coating again, the electroplate liquid of described 4th layer of nickel rifle color coating comprises: stannous pyrophosphate 50 grams per liter, nickelous chloride 45 grams per liter, potassium pyrophosphate 280 grams per liter, glycine 20 grams per liter.PH=8.7, temperature 20 DEG C, electroplate 3 minutes coating binding forces good, cross cut test is qualified, and Corrosion Protection is see table 1.

Embodiment 5

Will sintered Nd-Fe-B permanent magnetic material 2.3 kilograms of elder generations in vibrating ball mill, polish 2 hours.Through sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after sodium hydroxide 10g/ rises degreasing degreasing, pickling removing oxide on surface in 1% nitric acid, washing, plating the first layer nickel coating, electronickelling is Common platings watt nickel, plating solution formula is as follows: single nickel salt 275 grams per liter, nickelous chloride 30 grams per liter, boric acid 40 grams per liter, pH4.5, temperature 50 C, nickel concentration is 2.0mol/ liter, electronickelling thickness 5 microns.

With after washing, adopt electroplating copper pyrophosphate plating second layer copper coating, cupric pyrophosphate formula is as follows: cupric pyrophosphate 75 grams per liter, potassium pyrophosphate 320 grams per liter, and copper concentration is 0.5mol/ liter, pH8.5, temperature 55 DEG C, thickness of coating 8 microns.

Then, adopt bright nickel electroplate liquid plating third layer nickel coating, bright nickel electroplate liquid formulation following single nickel salt 275 grams per liter, nickelous chloride 30 grams per liter, boric acid 40 grams per liter, pH4.5, temperature 60 C, nickel concentration is 2.0mol/ liter, interpolation Atotech light external additive W-100A0.5 milliliter/liter, 100-B3 milliliter/liter, Y191.5 milliliter/liter; Electroplating bright nickel coating thickness 12 microns.

After washing, after third layer nickel coating plates the 4th layer of rifle color coating again, the electroplate liquid of described 4th layer of nickel rifle color coating comprises: stannous pyrophosphate 40 ~ 60 grams per liter, nickelous chloride 40 grams per liter, potassium pyrophosphate 280 grams per liter, glycine 20 grams per liter.PH=8.7, temperature 25 DEG C, electroplate 3 minutes, coating binding force is good, and cross cut test is qualified, and Corrosion Protection is see table 1.

Comparative example 1

Will sintered Nd-Fe-B permanent magnetic material 2.3 kilograms of elder generations in vibrating ball mill, polish 2 hours.Through sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after sodium hydroxide 10g/ rises degreasing degreasing, pickling removing oxide on surface in 1% nitric acid, washing, plating the first layer nickel, electronickelling is Common platings watt nickel, plating solution formula is as follows: single nickel salt 275 grams per liter, nickelous chloride 30 grams per liter, boric acid 40 grams per liter, pH3.5, temperature 60 C, nickel concentration is 2.0mol/ liter, electronickelling thickness 5 microns, washing, electroplating copper pyrophosphate, cupric pyrophosphate formula is as follows: cupric pyrophosphate 75 grams per liter, potassium pyrophosphate 280 grams per liter, copper concentration is 0.5mol/ liter, pH8.5, temperature 55 DEG C, thickness of coating 9 microns, electronickelling is semi-bright nickel, plating solution formula following single nickel salt 200 grams per liter, nickelous chloride 30 grams per liter, boric acid 40 grams per liter, pH4.0, temperature 60 C, nickel concentration is 1.5mol/ liter, interpolation Atotech half brightener M-9010.5 milliliter/liter, M902 volume 0.5 milliliter/liter, NP-A1.5 milliliter/liter, electronickelling is bright nickel, plating solution formula following single nickel salt 275 grams per liter, nickelous chloride 30 grams per liter, boric acid 40 grams per liter, pH3.5, temperature 60 C, nickel concentration is 2.0mol/ liter, interpolation Atotech light external additive W-100A0.5 milliliter/liter, 100-B3 milliliter/liter, Y191.5 milliliter/liter:, plating semi-bright nickel and bright nickel coat-thickness 12 microns.

Electroplate rear anticorrosion test by table 1 identical with shooting of multi-layer nickel electroplating with bonding force (PCT high temperature and pressure test temperature 120 DEG C, 2 normal atmosphere, relative humidity 100%), but tin-nickel alloy can reduce the glossiness of electric bright nickel plating, reduce nickel irritated.

It should be noted that, foregoing invention content and embodiment are intended to the practical application proving technical scheme provided by the present invention, should not be construed as limiting the scope of the present invention.Those skilled in the art in spirit of the present invention and principle, when doing various amendment, equivalent replace or improve.Protection scope of the present invention is as the criterion with appended claims.

Claims (6)

1. have a rare-earth permanent magnet for MULTILAYER COMPOSITE electrolytic coating, described rare-earth permanent magnet comprises rare-earth permanent magnet, the first layer nickel coating, second layer copper coating, third layer nickel coating, the 4th layer of gun barrel RIFLE tin nickel dam; Wherein, coating total thickness is not more than 30 μm, thickness≤5 μm of the first layer, thickness≤10 μm of the described second layer, thickness≤20 μm of third layer; The electroplate liquid of described 4th layer of rifle look tin-nickel coating comprises: stannous pyrophosphate 40 ~ 60 grams per liter, nickelous chloride 30 ~ 45 grams per liter, potassium pyrophosphate 250 ~ 320 grams per liter, glycine 20 grams per liter.
2. rare-earth permanent magnet according to claim 1, wherein, the electroplating time of described 4th layer of rifle look tin-nickel coating is 1 ~ 5 point, and the pH of described electroplate liquid is 7.0 ~ 8.5.
3. rare-earth permanent magnet according to claim 1, wherein, described the first layer nickel coating adopts the formula of watt nickel to obtain, and wherein, the pH value range of described electroplate liquid is 3.5 ~ 5.5, and temperature range is 35 ~ 60 DEG C, and Ni 2+concentration range is 1.0 ~ 2.0mol/L; The electroplate liquid of described second layer copper coating adopts the formula of cupric pyrophosphate plating solution to obtain, and wherein, the pH value range of described electroplate liquid is 7.0 ~ 9.5, and temperature range is 35 ~ 60 DEG C, and Cu 2+concentration range is 0.3 ~ 0.6mol/L; The electroplate liquid of described third layer nickel coating adopts commercially available brightening agent to be mixed with semi-bright nickel electroplate liquid and/or bright nickel electroplate liquid, and wherein, the pH value range of described semi-bright nickel electroplate liquid is 4.0, and temperature range is 60 DEG C, and Ni 2+concentration range is 1.5 ~ 2.0mol/L; The pH value range of described bright nickel electroplate liquid is 3.5 ~ 4.5, and temperature range is 60 DEG C, and Ni 2+concentration range is 2.0mol/L.
4. rare-earth permanent magnet as described in as arbitrary in claims 1 to 3 carries out a composite electric plating method, described method comprises the steps:
(1) adopt mechanical vibration, barreling chamfering to Nd-Fe-Bo permanent magnet material carry out routine polishing;
(2) degreasing degreasing: add alkaline degreaser and carry out conventional degreasing degreasing;
(3) acid pickling and rust removing: add acidic solution again and carry out conventional acid pickling and rust removing;
(4) four layers of composite plating: first plate the first layer nickel coating, then plate second layer copper coating, second layer copper coating plates third layer nickel coating and
(5) finally the 4th layer of rifle look tin-nickel coating is plated again;
Wherein, coating total thickness is not more than 30 μm, and the electroplate liquid of described 4th layer of rifle look tin-nickel coating comprises: stannous pyrophosphate 40 ~ 60 grams per liter, nickelous chloride 30 ~ 45 grams per liter potassium pyrophosphate, 250 ~ 320 grams per liters, glycine 20 grams per liter.
5. method according to claim 4, wherein, the electroplating time of described 4th layer of nickel coating is 1 ~ 5 point, and the pH of described electroplate liquid is 7.0 ~ 8.5.
6. method according to claim 4, wherein, described the first layer nickel coating adopts the formula of watt nickel to obtain, and wherein, the pH value range of described electroplate liquid is 3.5 ~ 5.5, and temperature range is 35 ~ 60 DEG C, and Ni 2+concentration range is 1.0 ~ 2.0mol/L; The electroplate liquid of described second layer copper coating adopts the formula of cupric pyrophosphate plating solution to obtain, and wherein, the pH value range of described electroplate liquid is 7.0 ~ 9.5, and temperature range is 35 ~ 60 DEG C, and Cu 2+concentration range is 0.3 ~ 0.6mol/L; The electroplate liquid of described third layer nickel coating adopts commercially available brightening agent to be mixed with semi-bright nickel electroplate liquid and/or bright nickel electroplate liquid, and wherein, the pH value range of described semi-bright nickel electroplate liquid is 4.0, and temperature range is 60 DEG C, and Ni 2+concentration range is 1.5 ~ 2.0mol/L; The pH value range of described bright nickel electroplate liquid is 3.5 ~ 4.5, and temperature range is 60 DEG C, and Ni 2+concentration range is 2.0mol/L.
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