CN104630852B - Rare-earth permanent magnet and its composite electric plating method with MULTILAYER COMPOSITE electroplated layer - Google Patents

Rare-earth permanent magnet and its composite electric plating method with MULTILAYER COMPOSITE electroplated layer Download PDF

Info

Publication number
CN104630852B
CN104630852B CN201310560338.8A CN201310560338A CN104630852B CN 104630852 B CN104630852 B CN 104630852B CN 201310560338 A CN201310560338 A CN 201310560338A CN 104630852 B CN104630852 B CN 104630852B
Authority
CN
China
Prior art keywords
layer
nickel
coating
electroplate liquid
grams per
Prior art date
Application number
CN201310560338.8A
Other languages
Chinese (zh)
Other versions
CN104630852A (en
Inventor
白晓刚
Original Assignee
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 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 filed Critical 天津三环乐喜新材料有限公司
Priority to CN201310560338.8A priority Critical patent/CN104630852B/en
Publication of CN104630852A publication Critical patent/CN104630852A/en
Application granted granted Critical
Publication of CN104630852B publication Critical patent/CN104630852B/en

Links

Classifications

    • 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 present invention provides a kind of rare-earth permanent magnet and its composite electric plating method with MULTILAYER COMPOSITE electroplated layer, the rare-earth permanent magnet with MULTILAYER COMPOSITE electroplated layer include rare-earth permanent magnet, first layer nickel coating, second layer copper coating, the 4th layer of third layer nickel coating for electroplate liquid include: 40~60 grams per liter of stannous pyrophosphate, 30~45 grams per liter potassium pyrophosphate of nickel chloride, 250~320 grams per liters, 20 grams per liter of glycine.The 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, and color is shiny black certain decorative effect.

Description

Rare-earth permanent magnet and its composite electric plating method with MULTILAYER COMPOSITE electroplated layer

Technical field

The present invention relates to the field of surface treatment of material, more particularly, to the rare-earth permanent magnet with MULTILAYER COMPOSITE electroplated layer And its composite electric plating method.

Background technique

The application and development of neodymium iron boron (NdFeB) permanent-magnet material are very rapid in recent years, and Nd-Fe-B permanent magnet material is anti- Shield success or not is related to one of the key technology that can material promote and apply.The material is mainly by rare earth metal neodymium Nd, iron It is prepared with elements such as boron by powder metallurgical technique.As current strongest magnetic material, have been widely used for being electroplated All fields such as device, machinery, medical treatment, automobile, application prospect are very wide.

The premise of Nd-Fe-B permanent magnet material application is the Anticorrosion for first having to resolve Nd-Fe-B permanent magnet material.As one The porous material that kind powder metallurgical technique is prepared, because of Nd-rich phase therein, neodymium iron boron main phase and boundary are mutually readily formed Intercrystalline corrosion.Rear earth element nd in neodymium iron boron powder metallurgy, property is active, becomes the corrosion resisting property of entire Nd Fe B alloys Very poor, the easily corrosion in damp and hot environment has seriously affected neodymium because of the decline or damage of magnetic property caused by corrosion failure The service life of iron boron permanent magnet reduces the stability and reliability of product.The magnetic property of Nd-Fe-B permanent magnet material and its group Knitting structure has very big relationship.The main phase of Nd-Fe-B permanent magnet is the main source of magnet magnetic property.Coercivity is contributed maximum Be Nd-rich phase.Huge variation will occur for the magnetic property of material after Nd-Fe-B permanent magnet material occurs to corrode.Therefore, neodymium iron The Anticorrosion of B permanent magnetic material is always the main problem that Nd-Fe-B permanent magnet material needs to solve.

The anti-corrosion method of Nd-Fe-B permanent magnet material has much at present.Wherein have electronickelling, electrogalvanizing (CN1421547A, CN1056133A), shooting of multi-layer nickel electroplating (CN102568732CN200910244404), copper facing (CN1514889A), phosphatization (CN101022051), a variety of methods such as electrophoretic paint.

Currently, Nd-Fe-B permanent magnet is more applied in consumer electronics product, and the general body of consumer electronics product Product is small, is tested using the method for artificial detection to bad products.General Nd-Fe-B permanent magnet uses the method table of electronickelling Face is bright, and inspector examines for a long time to cause adverse effect to eyes etc..

Summary of the invention

In order to overcome the above-mentioned problems of the prior art, the present invention provides a kind of with the dilute of MULTILAYER COMPOSITE electroplated layer Native permanent magnet, and composite electric plating method is carried out on the permanent magnet, which can not only play conventional electronickelling Anticorrosion ability, and have certain protection for the eyes of inspector, and appearance uniform, color is shiny black certain dress Adorn effect.

According to an aspect of the present invention, the present invention provides a kind of rare-earth permanent magnet with MULTILAYER COMPOSITE electroplated layer, institutes Stating the rare-earth permanent magnet with MULTILAYER COMPOSITE electroplated layer includes rare-earth permanent magnet, first layer nickel coating, second layer copper coating, third Layer nickel coating, the 4th layer of gun barrel RIFLE tin-nickel coating；Wherein, coating overall thickness is no more than 30 μm, thickness≤5 μm of first layer, institute State thickness≤10 μm of the second layer, thickness≤20 μm of third layer；The electroplate liquid of the 4th layer of gun barrel RIFLE tin-nickel coating includes: 40~60 grams per liter of stannous pyrophosphate, 30~45 grams per liter of nickel chloride, 250~320 grams per liter of potassium pyrophosphate, 20 grams per liter of glycine.

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

Preferably, the first layer nickel coating is made using the formula of watt nickel, wherein the pH value model of the electroplate liquid Enclosing is 3.5~5.5, and temperature range is 35~60 DEG C, and Ni2+Concentration range is 1.0~2.0mol/L；The second layer copper plating The electroplate liquid of layer is made using the formula of cupric pyrophosphate plating solution, wherein the pH value range of the electroplate liquid is 7.0~9.5, temperature Spending range is 35~60 DEG C, and Cu2+Concentration range is 0.3~0.6mol/L；The electroplate liquid of the third layer nickel coating is to adopt Semi-bright nickel electroplate liquid and/or bright nickel plating solution are configured to commercially available brightener, wherein the pH of the semi-bright nickel electroplate liquid Being worth range is 4.0, and temperature range is 60 DEG C, and Ni2+Concentration range is 1.5~2.0mol/L；The light nickel plating solution PH value range is 3.5~4.5, and temperature range is 60 DEG C, and Ni2+Concentration range is 2.0mol/L.

According to another aspect of the present invention, the present invention also provides a kind of on rare-earth permanent magnet carries out the side of composite plating Method, described method includes following steps: (1) carrying out conventional polishing to Nd-Fe-B permanent magnet material using mechanical vibration, barreling chamfering； (2) degreasing degreasing: alkaline degreaser is added and carries out conventional degreasing degreasing；(3) it acid pickling and rust removing: adds acid solution and carries out routine Acid pickling and rust removing；(4) four layers of composite plating: first layer nickel coating is first plated, then plates second layer copper coating, is plated on second layer copper coating The 4th layer of gun barrel RIFLE tin-nickel coating is finally plated in third layer nickel coating and (5) again.Wherein, coating overall thickness is not more than 30 μm, institute The electroplate liquid for stating the 4th layer of gun barrel RIFLE tin-nickel coating includes: 40~60 grams per liter of stannous pyrophosphate, nickel chloride 30~45 grams per liter coke Potassium phosphate, 250~320 grams per liters, 20 grams per liter of glycine.

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

Preferably, the first layer nickel coating is made using the formula of watt nickel, wherein the pH value model of the electroplate liquid Enclosing is 3.5~5.5, and temperature range is 35~60 DEG C, and Ni2+Concentration range is 1.0~2.0mol/L；The second layer copper plating The electroplate liquid of layer is made using the formula of cupric pyrophosphate plating solution, wherein the pH value range of the electroplate liquid is 7.0~9.5, temperature Spending range is 35~60 DEG C, and Cu2+Concentration range is 0.3~0.6mol/L；The electroplate liquid of the third layer nickel coating is to adopt Semi-bright nickel electroplate liquid and/or bright nickel plating solution are configured to commercially available brightener, wherein the pH of the semi-bright nickel electroplate liquid Being worth range is 4.0, and temperature range is 60 DEG C, and Ni2+Concentration range is 1.5~2.0mol/L；The light nickel plating solution PH value range is 3.5~4.5, and temperature range is 60 DEG C, and Ni2+Concentration range is 2.0mol/L.

The method that a kind of MULTILAYER COMPOSITE plating provided by the invention improves rare-earth permanent magnet corrosion resistance of surface, with the prior art It compares, which can not only play the anticorrosion ability of conventional electronickelling, and have centainly for the eyes of inspector Protection, and appearance uniform, color is shiny black certain decorative effect.After this treatment, binding force and electronickelling phase is electroplated Together, and anti-corrosion ability is identical as shooting of multi-layer nickel electroplating.Salt spray test was up to 48 hours.The present invention has filled up domestic Nd-Fe-B permanent magnet material The blank of surface treatment.

Detailed description of the invention

Fig. 1 is the coating composition shown using Electronic Speculum to outermost layer gun barrel RIFLE coating energy spectrum diagram.

Specific embodiment

Below with reference to embodiment, the present invention will be further described, and the embodiment of the present invention is merely to illustrate of the invention Technical solution, and the non-limiting present invention.

Embodiment 1

It will2.3 kilograms of elder generations of sintered Nd-Fe-B permanent magnetic material polished in vibrating ball-mill 2 hours.Through Sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after sodium hydroxide 10g/ rises degreasing degreasing, pickling removes Surface Oxygen in 1% nitric acid First layer nickel coating is electroplated in compound, washing, and electronickelling is Common platings watt nickel, and plating solution formula is as follows: 275 grams of nickel sulfate/ It rises, 30 grams per liter of nickel chloride, 40 grams per liter of boric acid, pH 3.5, temperature 60 C, nickel concentration is 2.0mol/ liter, and electronickelling thickness 5 is micro- Rice.

Second layer copper coating is electroplated using electroplating copper pyrophosphate in then washing, and cupric pyrophosphate formula is as follows: cupric pyrophosphate 90 Grams per liter, 320 grams per liter of potassium pyrophosphate, copper concentration be 0.6mol/ liter, pH 7.0,55 DEG C of temperature, 7 microns of thickness of coating.

Then, using bright nickel plating solution be electroplated third layer nickel coating, 275 grams of the following nickel sulfate of bright nickel electroplate liquid formulation/ It rises, 30 grams per liter of nickel chloride, 40 grams per liter of boric acid, pH 3.5, temperature 60 C, nickel concentration is 2.0mol/ liter, and addition Atotech is bright 0.5 ml l of external additive W-100A, 3 ml ls of 100-B, 1.5 ml ls of Y19: electroplating bright nickel coating thickness 10 Micron.

After washing, after plating the 4th layer of gun barrel RIFLE coating again on third layer nickel coating, the 4th layer of nickel gun barrel RIFLE plating Layer electroplate liquid include: 40 grams per liter of stannous pyrophosphate, 30 grams per liter of nickel chloride, 250 grams per liter of potassium pyrophosphate, 20 grams of glycine/ It rises.1 minute pH=8.5 is electroplated, 20 DEG C of temperature, coating binding force is good, and cross cut test is qualified, and Corrosion Protection is referring to table 1.It is outermost The coating composition that layer gun barrel RIFLE coating energy spectrum diagram is shown is referring to Figure 1.

Embodiment 2

It will2.3 kilograms of elder generations of sintered Nd-Fe-B permanent magnetic material polished in vibrating ball-mill 2 hours.Through Sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after sodium hydroxide 10g/ rises degreasing degreasing, pickling removes Surface Oxygen in 1% nitric acid First layer nickel coating is electroplated in compound, washing, and electronickelling is Common platings watt nickel, and plating solution formula is as follows: 150 grams of nickel sulfate/ It rises, 20 grams per liter of nickel chloride, 40 grams per liter of boric acid, pH 4.5,35 DEG C of temperature, nickel concentration is 1.0mol/ liter, and electronickelling thickness 3 is micro- Rice.

Second layer copper coating is electroplated using electroplating copper pyrophosphate in then washing, and cupric pyrophosphate formula is as follows: cupric pyrophosphate 45 Grams per liter, 240 grams per liter of potassium pyrophosphate, copper concentration be 0.3mol/ liter, pH 9.5, temperature 60 C, 10 microns of thickness of coating.

Then, using bright nickel plating solution be electroplated third layer nickel coating, 275 grams of the following nickel sulfate of bright nickel electroplate liquid formulation/ It rises, 30 grams per liter of nickel chloride, 40 grams per liter of boric acid, pH 3.5, temperature 60 C, nickel concentration is 2.0mol/ liter, and addition Atotech is bright 0.5 ml l of external additive W-100A, 3 ml ls of 100-B, 1.5 ml ls of Y19: electroplating bright nickel coating thickness 15 Micron.

After washing, after plating the 4th layer of gun barrel RIFLE coating again on third layer nickel coating, the 4th layer of nickel gun barrel RIFLE plating Layer electroplate liquid include: 60 grams per liter of stannous pyrophosphate, 45 grams per liter of nickel chloride, 320 grams per liter of potassium pyrophosphate, 20 grams of glycine/ It rises.25 DEG C of pH=8.5 temperature plating, 3 minutes coating binding forces are good, and cross cut test is qualified, and Corrosion Protection is referring to table 1.

Embodiment 3

It will2.3 kilograms of elder generations of sintered Nd-Fe-B permanent magnetic material polished in vibrating ball-mill 2 hours.Through Sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after sodium hydroxide 10g/ rises degreasing degreasing, pickling removes Surface Oxygen in 1% nitric acid First layer nickel coating is electroplated in compound, washing, and electronickelling is Common platings watt nickel, and plating solution formula is as follows: 200 grams of nickel sulfate/ It rises, 30 grams per liter of nickel chloride, 40 grams per liter of boric acid, pH 3.5,55 DEG C of temperature, nickel concentration is 1.5mol/ liter, and electronickelling thickness 4 is micro- Rice.

Second layer copper coating is electroplated using electroplating copper pyrophosphate in then washing, and cupric pyrophosphate formula is as follows: cupric pyrophosphate 75 Grams per liter, 280 grams per liter of potassium pyrophosphate, copper concentration be 0.5mol/ liter, pH 8.0,55 DEG C of temperature, 10 microns of thickness of coating.

Then, third layer nickel coating, the following nickel sulfate of semi-bright nickel electroplate liquid formulation are first electroplated using semi-bright nickel electroplate liquid 275 grams per liters, 30 grams per liter of nickel chloride, 40 grams per liter of boric acid, pH 4.0, temperature 60 C, nickel concentration are 2.0mol/ liter, addition peace beauty Special M-9010.5 ml ls of half brightener, 0.5 ml l of M902, NP-A1.5 milliliters/.Again using bright nickel plating solution Plating third layer nickel coating, following 275 grams per liter of nickel sulfate of bright nickel electroplate liquid formulation, 30 grams per liter of nickel chloride, 40 grams per liter of boric acid, PH 3.5, temperature 60 C, nickel concentration are 2.0mol/ liter, add W-100A0.5 ml ls of external additive of Atotech light, 100- 3 ml ls of B, 1.5 ml ls of Y19: plating semi-bright nickel and bright 15 microns of nickel coating thickness.

After washing, after plating the 4th layer of gun barrel RIFLE coating again on third layer nickel coating, the 4th layer of nickel gun barrel RIFLE plating Layer electroplate liquid include: 50 grams per liter of stannous pyrophosphate, 45 grams per liter of nickel chloride, 280 grams per liter of potassium pyrophosphate, 20 grams of glycine/ It rises.PH=8.6,24 DEG C of temperature, it is good to be electroplated 2 minutes coating binding forces, and cross cut test is qualified, and Corrosion Protection is referring to table 1.

Embodiment 4

It will2.3 kilograms of elder generations of sintered Nd-Fe-B permanent magnetic material polished in vibrating ball-mill 2 hours.Through Sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after sodium hydroxide 10g/ rises degreasing degreasing, pickling removes Surface Oxygen in 1% nitric acid First layer nickel coating is electroplated in compound, washing, and electronickelling is Common platings watt nickel, and plating solution formula is as follows: 275 grams of nickel sulfate/ It rises, 30 grams per liter of nickel chloride, 40 grams per liter of boric acid, pH 3.5, temperature 60 C, nickel concentration is 2.0mol/ liter, and electronickelling thickness 5 is micro- Rice.

Second layer copper coating is electroplated using electroplating copper pyrophosphate in then washing, and cupric pyrophosphate formula is as follows: cupric pyrophosphate 75 Grams per liter, 280 grams per liter of potassium pyrophosphate, copper concentration be 0.5mol/ liter, pH 8.5,55 DEG C of temperature, 9 microns of thickness of coating.

Then, third layer nickel coating, the following nickel sulfate of semi-bright nickel electroplate liquid formulation are first electroplated using semi-bright nickel electroplate liquid 200 grams per liters, 30 grams per liter of nickel chloride, 40 grams per liter of boric acid, pH 4.0, temperature 60 C, nickel concentration are 1.5mol/ liter, addition peace beauty Special M-9010.5 ml ls of half brightener, 0.5 ml l of M902, NP-A1.5 ml ls.It is electroplated again using bright nickel Liquid plating, following 275 grams per liter of nickel sulfate of bright nickel electroplate liquid formulation, 30 grams per liter of nickel chloride, 40 grams per liter of boric acid, pH 3.5, temperature 60 DEG C, nickel concentration be 2.0mol/ liter, add W-100A0.5 ml ls of external additive of Atotech light, 3 ml ls of 100-B, 1.5 ml ls of Y19: plating semi-bright nickel and bright 12 microns of nickel coating thickness.

After washing, after plating the 4th layer of gun barrel RIFLE coating again on third layer nickel coating, the 4th layer of nickel gun barrel RIFLE plating Layer electroplate liquid include: 50 grams per liter of stannous pyrophosphate, 45 grams per liter of nickel chloride, 280 grams per liter of potassium pyrophosphate, 20 grams of glycine/ It rises.PH=8.7,20 DEG C of temperature, it is good to be electroplated 3 minutes coating binding forces, and cross cut test is qualified, and Corrosion Protection is referring to table 1.

Embodiment 5

It will2.3 kilograms of elder generations of sintered Nd-Fe-B permanent magnetic material polished in vibrating ball-mill 2 hours.Through Sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after sodium hydroxide 10g/ rises degreasing degreasing, pickling removes Surface Oxygen in 1% nitric acid First layer nickel coating is electroplated in compound, washing, and electronickelling is Common platings watt nickel, and plating solution formula is as follows: 275 grams of nickel sulfate/ It rises, 30 grams per liter of nickel chloride, 40 grams per liter of boric acid, pH 4.5, temperature 50 C, nickel concentration is 2.0mol/ liter, and electronickelling thickness 5 is micro- Rice.

Second layer copper coating is electroplated using electroplating copper pyrophosphate in then washing, and cupric pyrophosphate formula is as follows: cupric pyrophosphate 75 Grams per liter, 320 grams per liter of potassium pyrophosphate, copper concentration be 0.5mol/ liter, pH 8.5,55 DEG C of temperature, 8 microns of thickness of coating.

Then, using bright nickel plating solution be electroplated third layer nickel coating, 275 grams of the following nickel sulfate of bright nickel electroplate liquid formulation/ It rises, 30 grams per liter of nickel chloride, 40 grams per liter of boric acid, pH 4.5, temperature 60 C, nickel concentration is 2.0mol/ liter, and addition Atotech is bright 0.5 ml l of external additive W-100A, 3 ml ls of 100-B, 1.5 ml ls of Y19；Electroplating bright nickel coating thickness 12 Micron.

After washing, after plating the 4th layer of gun barrel RIFLE coating again on third layer nickel coating, the 4th layer of nickel gun barrel RIFLE plating The electroplate liquid of layer includes: 40~60 grams per liter of stannous pyrophosphate, 40 grams per liter of nickel chloride, 280 grams per liter of potassium pyrophosphate, glycine 20 Grams per liter.PH=8.7, is electroplated 3 minutes by 25 DEG C of temperature, and coating binding force is good, and cross cut test is qualified, and Corrosion Protection is referring to table 1.

Comparative example 1

It will2.3 kilograms of elder generations of sintered Nd-Fe-B permanent magnetic material polished in vibrating ball-mill 2 hours.Through Sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after sodium hydroxide 10g/ rises degreasing degreasing, pickling removes Surface Oxygen in 1% nitric acid First layer nickel is electroplated in compound, washing, and electronickelling is Common platings watt nickel, and plating solution formula is as follows: 275 grams per liter of nickel sulfate, 30 grams per liter of nickel chloride, 40 grams per liter of boric acid, pH 3.5, temperature 60 C, nickel concentration be 2.0mol/ liter, 5 microns of electronickelling thickness, Washing, electroplating copper pyrophosphate, cupric pyrophosphate formula are as follows: 75 grams per liter of cupric pyrophosphate, 280 grams per liter of potassium pyrophosphate, copper concentration are 0.5mol/ liter, pH 8.5,55 DEG C of temperature, 9 microns of thickness of coating, electronickelling is semi-bright nickel, the following nickel sulfate of plating solution formula 200 grams per liters, 30 grams per liter of nickel chloride, 40 grams per liter of boric acid, pH 4.0, temperature 60 C, nickel concentration are 1.5mol/ liter, addition peace beauty 0.5 ml l of half brightener M-901 of spy, 0.5 ml l of M902 volume, NP-A1.5 ml ls, electronickelling is light Nickel, following 275 grams per liter of nickel sulfate of plating solution formula, 30 grams per liter of nickel chloride, 40 grams per liter of boric acid, pH 3.5, temperature 60 C, nickel Concentration be 2.0mol/ liter, add W-100A0.5 ml ls of external additive of Atotech light, 3 ml ls of 100-B, Y19 1.5 Ml l:, plating semi-bright nickel and bright 12 microns of nickel coating thickness.

(120 DEG C of PCT high temperature and pressure test temperature, 2 atmospheric pressure are relatively wet for anticorrosion test and binding force after being electroplated by table 1 Degree is 100%) identical as shooting of multi-layer nickel electroplating, but tin-nickel alloy can reduce the glossiness of electric bright nickel plating, reduces nickel allergy.

It should be noted that foregoing invention content and specific embodiment are intended to prove technical solution provided by the present invention Practical application should not be construed as limiting the scope of the present invention.Those skilled in the art are in spirit and principles of the present invention It is interior, when can various modifications may be made, equivalent replacement or improve.Protection scope of the present invention is subject to the appended claims.

Claims (6)

1. a kind of rare-earth permanent magnet with MULTILAYER COMPOSITE electroplated layer, the rare-earth permanent magnet packet with MULTILAYER COMPOSITE electroplated layer Include rare-earth permanent magnet, first layer nickel coating, second layer copper coating, third layer nickel coating, the 4th layer of gun barrel RIFLE tin-nickel coating；Its In, coating overall thickness is no more than 30 μm, thickness≤5 μm of first layer, thickness≤10 μm of the second layer, the thickness of third layer ≤20μm；The electroplate liquid of the first layer nickel coating is made using the formula of watt nickel, and the temperature range of the electroplate liquid is 35~60 DEG C；The electroplate liquid of the second layer copper coating is made using the formula of cupric pyrophosphate plating solution, the temperature of the electroplate liquid Spending range is 35~60 DEG C；The electroplate liquid of the third layer nickel coating is to be configured to semi-bright nickel electroplate liquid using commercially available brightener And/or bright nickel plating solution, the temperature range of the semi-bright nickel electroplate liquid or bright nickel plating solution is 60 DEG C；Described 4th layer The electroplate liquid of gun barrel RIFLE tin-nickel coating includes: 40~60 grams per liter of stannous pyrophosphate, 30~45 grams per liter of nickel chloride, potassium pyrophosphate 250~320 grams per liters, 20 grams per liter of glycine, the temperature of the electroplate liquid of the 4th layer of gun barrel RIFLE tin-nickel coating are 20 DEG C, 24 ℃、25℃。
2. rare-earth permanent magnet according to claim 1, wherein the electroplating time of the 4th layer of gun barrel RIFLE tin-nickel coating is 1~5 minute, the pH of the electroplate liquid was 7.0~8.5.
3. rare-earth permanent magnet according to claim 1, wherein the pH value model of the electroplate liquid of the first layer nickel coating Enclosing is 3.5~5.5, and Ni2+Concentration range is 1.0~2.0mol/L；The pH of the electroplate liquid of the second layer copper coating Being worth range is 7.0~9.5, and Cu2+Concentration range is 0.3~0.6mol/L；Described the half of the third layer nickel coating is bright The pH value range of nickel plating solution is 4.0, and Ni2+Concentration range is 1.5~2.0mol/L；The pH value of the light nickel plating solution Range is 3.5~4.5, and Ni2+Concentration range is 2.0mol/L.
4. a kind of composite plating method for preparing the rare-earth permanent magnet as described in claims 1 to 3 is any, the composite plating method Include the following steps:
(1) conventional polishing is carried out to Nd-Fe-B permanent magnet material using mechanical vibration, barreling chamfering；
(2) degreasing degreasing: alkaline degreaser is added and carries out conventional degreasing degreasing；
(3) it acid pickling and rust removing: adds acid solution and carries out conventional acid pickling and rust removing；
(4) four layers of composite plating: first layer nickel coating is first plated, then plates second layer copper coating, plates third on second layer copper coating Layer nickel coating and
(5) the 4th layer of gun barrel RIFLE tin-nickel coating is finally plated again；
Wherein, coating overall thickness is not more than 30 μm, and the electroplate liquid of the first layer nickel coating is made using the formula of watt nickel, The temperature range of the electroplate liquid is 35~60 DEG C；The electroplate liquid of the second layer copper coating is matching using cupric pyrophosphate plating solution Side is made, and the temperature range of the electroplate liquid is 35~60 DEG C；The electroplate liquid of the third layer nickel coating is using commercially available light Agent is configured to semi-bright nickel electroplate liquid and/or bright nickel plating solution, the temperature of the semi-bright nickel electroplate liquid or bright nickel plating solution Spending range is 60 DEG C；The electroplate liquid of the 4th layer of gun barrel RIFLE tin-nickel coating includes: 40~60 grams per liter of stannous pyrophosphate, chlorination 30~45 grams per liter potassium pyrophosphate of nickel, 250~320 grams per liters, 20 grams per liter of glycine, the 4th layer of gun barrel RIFLE tin-nickel coating The temperature of electroplate liquid is 20 DEG C, 24 DEG C, 25 DEG C.
5. composite plating method according to claim 4, wherein the electroplating time of the 4th layer of nickel coating is 1~5 point Clock, the pH of the electroplate liquid are 7.0~8.5.
6. composite plating method according to claim 4, wherein the pH value of the electroplate liquid of the first layer nickel coating Range is 3.5~5.5, and Ni2+Concentration range is 1.0~2.0mol/L；The electroplate liquid of the second layer copper coating PH value range is 7.0~9.5, and Cu2+Concentration range is 0.3~0.6mol/L；The semi-gloss of the third layer nickel coating The pH value range of bright nickel plating solution is 4.0, and Ni2+Concentration range is 1.5~2.0mol/L；The pH of the light nickel plating solution Being worth range is 3.5~4.5, and Ni2+Concentration range is 2.0mol/L.
CN201310560338.8A 2013-11-12 2013-11-12 Rare-earth permanent magnet and its composite electric plating method with MULTILAYER COMPOSITE electroplated layer CN104630852B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310560338.8A CN104630852B (en) 2013-11-12 2013-11-12 Rare-earth permanent magnet and its composite electric plating method with MULTILAYER COMPOSITE electroplated layer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310560338.8A CN104630852B (en) 2013-11-12 2013-11-12 Rare-earth permanent magnet and its composite electric plating method with MULTILAYER COMPOSITE electroplated layer

Publications (2)

Publication Number Publication Date
CN104630852A CN104630852A (en) 2015-05-20
CN104630852B true CN104630852B (en) 2018-12-18

Family

ID=53210086

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310560338.8A CN104630852B (en) 2013-11-12 2013-11-12 Rare-earth permanent magnet and its composite electric plating method with MULTILAYER COMPOSITE electroplated layer

Country Status (1)

Country Link
CN (1) CN104630852B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105405562A (en) * 2015-12-01 2016-03-16 中磁科技股份有限公司 Neodymium-iron-boron magnet
CN109208047A (en) * 2018-08-08 2019-01-15 北京麦戈龙科技有限公司 A kind of coating structure of Sintered NdFeB magnet and preparation method thereof

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002126642A (en) * 2000-10-24 2002-05-08 Tdk Corp Magnetic kinetic mass part for mobile telecommunication equipment and method for producing the same
JP2006158012A (en) * 2004-11-25 2006-06-15 Honda Motor Co Ltd Method of manufacturing permanent magnet for use in ipm-type motor for automobile
CN101284436A (en) * 2007-04-13 2008-10-15 陈泰佐 Tool surface structure and handling method thereof
CN101280444B (en) * 2007-12-29 2010-11-24 横店集团东磁有限公司 Anticorrosive electroplating method for Nd-Fe-B magnet steel
CN102117692B (en) * 2009-12-30 2014-12-31 北京中科三环高技术股份有限公司 Rare-earth permanent magnet with multilayer composite electroplated coating and method for carrying out composite electroplating
CN102115899B (en) * 2010-01-05 2015-06-03 北京中科三环高技术股份有限公司 Tin-nickel alloy plating solution used for plating neodymium iron boron permanent magnet material and method for plating neodymium iron boron permanent magnet material by adopting same
CN202473461U (en) * 2012-02-22 2012-10-03 沈阳中北通磁科技股份有限公司 Multilayer-structure neodymium-iron-boron permanent magnet material
CN102586829B (en) * 2012-02-22 2015-04-22 沈阳中北通磁科技股份有限公司 Process method for reducing magnetic loss of neodymium-iron-boron permanent magnet under high-temperature and high-humidity conditions
CN102586776B (en) * 2012-02-22 2014-08-06 沈阳中北通磁科技股份有限公司 Surface coating process for neodymium iron boron permanent magnetic material and neodymium iron boron permanent magnetic material
CN102568732B (en) * 2012-02-22 2015-08-12 沈阳中北通磁科技股份有限公司 A kind of Nd-Fe-Bo permanent magnet material of sandwich construction and processing technology thereof

Also Published As

Publication number Publication date
CN104630852A (en) 2015-05-20

Similar Documents

Publication Publication Date Title
JP3354767B2 (en) Alkaline zinc and zinc alloy electroplating baths and processes
KR101554217B1 (en) 100-- AMORPHOUS Fe100-a-bPaMb ALLOY FOIL AND METHOD FOR ITS PREPARATION
Fleischmann et al. Raman spectroscopy of adsorbates on thin film electrodes deposited on silver substrates
Golodnitsky et al. Study of Nickel‐Cobalt Alloy Electrodeposition from a Sulfamate Electrolyte with Different Anion Additives
CN101532153B (en) Amorphous nano-alloy plating layer of electrodeposition nickel-based series, electroplating liquid and electroplating process
KR100921874B1 (en) Method for forming electroplated coating on surface of article
Mao et al. Corrosion behaviour of sintered NdFeB deposited with an aluminium coating
CN100494497C (en) Nickel pre-coating process and nickel pre-coating solution for magnesium alloy surface
CN102758230B (en) Gold electroplating solution and gold electroplating method
JP5762304B2 (en) Coated magnetic alloy material and manufacturing method thereof
CN100564607C (en) A kind of method of electroplating double-layer admiro film on Nd-Fe-B magnetic surface
CN103266312B (en) Magnesium lithium alloy surface chemical Ni-P-plating plating liquid and low temperature plating method thereof
CN102234802B (en) Method for preparing multilayer high corrosion resistant-wear resistant composite protective coating on magnesium alloy surface
CN102568738B (en) Manufacturing method of high-mechanical-strength sintered neodymium iron boron permanent magnets
CN102808210B (en) Micro-arc oxidation surface treatment method and product prepared by same
CN103668359A (en) Electroplating liquid of multi-layer cyanide-free electroplated copper-tin alloy coating, electroplating technology and coin thereof
CN100464007C (en) Process for preparing neodymium-iron-boron permanent magnetic material surface gradient function coating layer
JPWO2004079055A1 (en) Rare earth magnet manufacturing method and plating bath
JP2004516384A (en) Steel sheet and hot-dip steel sheet with excellent electric and magnetic shielding properties
TW201410924A (en) Surface treatment method for aluminum alloy parts for valves
CN102277601A (en) Cyanogen-free silver-plating electroplating liquid containing auxiliary complexing agent
CN105336490B (en) A kind of processing method of Nd-Fe-B permanent magnet
CN102041497A (en) Trivalent-chromium blue-white passivator for zinc-plated permanent magnetic material and passivation method thereof
JPWO2008146368A1 (en) Method for producing and using high corrosion resistance rare earth permanent magnet
CN102041506A (en) Surface treatment method of permanent magnet material

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant