CN1924110A - Metal based nano composite electric plating method for Nd-Fe-B material antisepsis - Google Patents
Metal based nano composite electric plating method for Nd-Fe-B material antisepsis Download PDFInfo
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- CN1924110A CN1924110A CN 200510032101 CN200510032101A CN1924110A CN 1924110 A CN1924110 A CN 1924110A CN 200510032101 CN200510032101 CN 200510032101 CN 200510032101 A CN200510032101 A CN 200510032101A CN 1924110 A CN1924110 A CN 1924110A
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Abstract
The invention discloses a metal based nanometer composite plating method of corrosion resistance Nd-Fe-B material, which is characterized by the following: removing oil for Nd-Fe-B working piece through ultrasound; brightening through dilute HNO3 solution; bleaching through clear water; placing in the composite nanometer plating groove to plate semi-light nickel; stripping film through electrolyzing; proceeding bright plating.
Description
Technical field
The invention belongs to the chemical surface treatment technical field, being specifically related to a kind of is the nano composite electric plating method of metal matrix with metals such as nickel, zinc, copper and nickel cobalt (alloy), Rhometal, nickel-phosphorus alloy.
Background technology
Neodymium in the Nd-Fe-B permanent magnet is a kind of rare earth element, and chemically reactive is very strong, and is easily oxidized in air, solidity to corrosion is poor, particularly there is rich neodymium phase in the Nd-Fe-B magnet, very easily produces intergranular corrosion, has the oxide compound of a large amount of neodymiums and hydride to form when serious and makes the material efflorescence; Secondly the most sintering processs that adopt of this class magneticsubstance prepare, and the surface has porousness, and fragility is big, and therefore short texture must carry out the special surface rotproofing to this class material.
So far, surface treatment method to the Nd-Fe-B permanent magnet, at first material being carried out sealing of hole handles, to avoid the residual of in oil removing, bright dipping and electroplating process subsequently basic intravital acid, alkali and plating bath, thereby avoid the internal corrosion of matrix, but this method effect is not clearly, and has increased the multiple tracks subsequent handling, has influenced working efficiency.Conventional ambrose alloy nickel or zincincation are still adopted in plating subsequently, and whole thickness of coating reaches more than the 20um at least; But conventional zinc-plated or nickel technology not only barrier propterty index does not reach high-quality requirement, and the whole process time often needs to reach nearly 4 hours (as the most frequently used barrel plating ambrose alloy nickel technology), also environment has been caused bigger influence (passivation of zinc needs sexavalent chrome) simultaneously.Chemical plating Mi-P alloy exists the life cycle weak point, costs an arm and a leg and a large amount of defectives such as sewage disposal.
Summary of the invention
In order to solve the anticorrosion problem of Nd-Fe-B material, the invention provides a kind of metal based nano composite electric plating method of the Nd-Fe-B of being used for material antiseptic, this method is by adding nanometer additive in electrodeposit liquid, not only can fully satisfy the anticorrosion and ornamental requirement of Nd-Fe-B workpiece, also substantially improved the surface evening effect of Nd-Fe-B workpiece, shortened whole process flow, saved expensive raw metal, and helped to reduce pollution environment.
A kind of metal based nano composite electric plating method that is used for the Nd-Fe-B material antiseptic through the ultrasonic wave oil removing, is used rare HNO with the Nd-Fe-B workpiece of need plating
3The solution bright dipping is put into nano combined coating bath and is carried out half light nickel plating after the clear water rinsing, carry out the electrolysis membrane removal after the half light nickel plating, carries out the bright nickel plating again.Concrete processing parameter is:
1. half light nickel plating
A) half light nickel plating bath component:
NiSO
4.6H
2O:200-400g/L, NiCl
2.6H
2O:35-80g/L, H
3BO
3: 35-55g/L, nanometer additive: 5～60mL/L;
B) anode: sulfur-bearing nickel plate or nickel cake;
C) negative electrode: Nd-Fe-B workpiece;
D) plating condition
Stir: pneumatic blending, pH:4.0-5.0, cathode current density: 2-5A/dm
2, temperature: 50-65 ℃;
2. electrolysis membrane removal
Voltage 4-6V, normal temperature, 30-60 second, catholyte, pure lead anode, electrolysis membrane removal in removing film.
The preparation method of described nanometer additive is: be the SiO of 10-100nm with granularity
2Nanoparticle and nonionogenic tenside mixing and ball milling, blending ratio is a nanoparticle: nonionogenic tenside=1: 0.5-10, then this mixture is mixed with cats product, water, blending ratio is a mixture: cats product: water=1: 0.2-3: 0.1-10 carries out batch mixing, strong shearing mechanism dispersed with stirring can obtain electroplating and use nanometer additive.
The nanometer additive using method: during plating, be warming up to technological temperature earlier, start pneumatic blending then, be added into tank liquor by 10-50mL nanometer additive/L, pneumatic blending is 30 minutes at least, gets final product plating.
In order to realize multi-functional material surface performance, nanoparticle can also be nano SiC or nanometer ZrO
2Or Nano diamond.Can add a kind of simultaneously or several nanoparticles, as adding nanometer SiO
2, can increase the solidity to corrosion of coating; Add nano SiC, can improve the hardness of this composite deposite; Add ZrO
2, can obtain the composite deposite of resistance to high temperature oxidation; Add Nano diamond, then can obtain the composite deposite surface of not only wear-resisting but also ultrahigh hardness.
The described preparation method who removes film is: in concentration expressed in percentage by weight is in the saline solution of haloid element of 0.1%-20%, adds the sulfuric acid of 1-30%.
Described nonionogenic tenside is that structure is the A1-A2-A3-H type, wherein A1 is the alkyl of 8-18 carbon-chain structure, A2 is the structure of independent oxygen or the oxygen that links to each other with phenyl ring, and A3 is the polymer-based group that contains oxyethyl group of 3-18 carbon-chain structure, and H is meant hydrogen atom.
Described cats product is meant that structure is the B1-B2-B3-X-M type, and wherein B1 is the alkyl group of 8-20 carbon-chain structure, and B2 is the group of 1-3 methyl structural, and B3 is benzyl or do not have group, and X is a haloid element, and M is ammonium, sodium cation.
Employing is used for the anticorrosion of NdFeB material by half light nickel composite deposite of the additive preparation that contains nano material provided by the invention and bright nickel layer electroplating technology or other metal matrix composite deposites (as nanometer zinc composite deposite etc.), not only can fully satisfy the anticorrosion and ornamental requirement of Nd-Fe-B workpiece, also substantially improved the surface evening effect of Nd-Fe-B workpiece, shortened whole process flow, saved expensive raw metal, and helped to reduce pollution environment.
By being joined, nanoparticle carries out ball milling and powerful mechanical stirring in the tensio-active agent, prepared and to make nano particle keep the nanometer additive that suspends always, the difficult problem during nanometer such as solved the homodisperse of nanoparticle in high density ionogen plating bath and do not reunite in discharge process is electroplated;
After the neodymium iron boron workpiece entered plating bath, nanoparticle can preferentially also enter in the thin hole of workpiece surface automatically, had driven away the solution that exists in the thin hole on the one hand, prevented that solution is in the intravital corrosion of base; Owing to filled the space, make coating have extremely good leveling effect, the barrier propterty that has further prolonged workpiece on the other hand;
Adopt the present invention to remove film, in one minute, can remove rete, thereby reached the purpose of activation coating, guaranteed plating of bright nickel subsequently and the excellent combination power between the double-deck nickel;
Embodiment
Embodiment 1:
With granularity is the SiO of 10-100nm
2Join in the nonionogenic tenside in 1: 1 ratio, mixing and ball milling at least 1 hour joins in the cats product and water of equal volume amount then, and strong shearing mechanism dispersed with stirring 1 hour can obtain nanometer additive.
Embodiment 2:
With granularity is the SiO of 10-100nm
2Join in the nonionogenic tenside in 1: 10 ratio, mixing and ball milling 5 hours joins the ratio of this compound material in 1: 0.1: 1 in cats product and the water then, and strong shearing mechanism dispersed with stirring 5 hours can obtain nanometer additive.
Embodiment 3:
Sulfuric acid 50 grams, sodium-chlor 5 grams, stirring fully is dissolved in and is dissolved in 1000 ml waters, must remove film.
Embodiment 4:
Sulfuric acid 200 grams, Sodium Fluoride 10 grams, stirring fully is dissolved in and is dissolved in 1000 ml waters, must remove film.
Embodiment 4:
1. half light nickel plating bath is filled a prescription
NiSO
4.6H
2O:350g/L, NiCl
2.6H
2O:60g/L, H
3BO
3: 45g/L, adopt embodiment 1 described nanometer additive, addition is 5mL/L;
2. plating condition
Anode: sulfur-bearing nickel plate or nickel cake, negative electrode: the Nd-Fe-B workpiece, stir: pneumatic blending, pH:4.0-5.0, cathode current density: 2-5A/dm
2, temperature: 50-65 ℃;
3. electrolysis membrane removal
Voltage 4-6V, normal temperature, 30-60 second, catholyte, pure lead anode adopts the embodiment 3 described films that remove.
4. bright nickel technology
Identical with routine, electroplating time 8-12 minute, barrel plating 0.5-1 hour.
5. result
The nanometer half light nickel composite deposite and the bright nickel layer of plating on the neodymium iron boron workpiece has good leveling effect and ornamental, carries out corrosion test with the 6B/T10125-1997 standard, and anti-neutral salt spray can reach more than 240 hours at least.The industry default standard is adopted in bonding force and seal (tightness)test, pressure 0.15MPa, T=125 ℃, t=100h, non-foaming, not sudden and violent skin of coating and non-corroding point.Or thermal shock test: T=250 ℃, the t=15 branch is put into 0 ℃ of frozen water then rapidly, the t=15 branch, and 5 circulations, test rear surface state: coating is non-foaming, nothing is peeled off, the non-corroding point.
Embodiment 6
1. the nickel cobalt (alloy) composite plating bath is filled a prescription
NiSO
4.6H
2O:200g/L, NaCl:11g/L, CoSO
4.7H
2O:8g/L, H
3BO
3: 30g/L, Na
2SO
4.10H
2O:27g/L adopts embodiment 2 described nanometer additives, and addition is 50mL/L;
2. plating condition
Anode: sulfur-bearing nickel plate or nickel cake, negative electrode: the Nd-Fe-B workpiece, stir: pneumatic blending, pH:5.0-6.0, cathode current density: 0.5-1.5A/dm
2, temperature: 35-40 ℃, electroplating time: decide general 8-15 minute on processing requirement;
3. electrolysis membrane removal
Voltage 4-6V, normal temperature, 30-60 second, catholyte, pure lead anode adopts the embodiment 4 described films that remove.
4. bright nickel technology
Identical with routine, rack plating electroplating time 8-12 minute.
5. result
Nickel cobalt (alloy) composite deposite/the bright nickel layer that obtains on the neodymium iron boron surface, the complete and common decoration nickel dam of its appearance luster is identical, but its solidity to corrosion is better, detects by national standard can reach neutral salt spray equally at least more than 240 hours.
Embodiment 7
1. the nano composite plating zinc electrolytic solution is filled a prescription
ZnCl
2: 70g/L, KCl:200g/L, H
3BO
3: 30g/L, adopt embodiment 1 described nanometer additive, addition is 20mL/L,
2. plating condition
Anode: pure zine plate, negative electrode: the Nd-Fe-B workpiece, stir: pneumatic blending, pH:4.5-6.0, cathode current density: 1-4A/dm
2, temperature: 10-40 ℃;
3. result
The zinc composite deposite that obtains on the neodymium iron boron surface, the common zinc coating unanimity of its appearance luster fundamental sum, bonding force is good, and solidity to corrosion is better.
Claims (4)
1. metal based nano composite electric plating method that is used for the Nd-Fe-B material antiseptic, it is characterized in that: the Nd-Fe-B workpiece that will need plating is used rare HNO through the ultrasonic wave oil removing
3The solution bright dipping is put into nano combined coating bath and is carried out half light nickel plating after the clear water rinsing, carry out the electrolysis membrane removal after the half light nickel plating, carries out the bright nickel plating again; Concrete processing parameter is:
1) half light nickel plating
A) half light nickel plating bath component:
NiSO
4.6H
2O:200-400g/L, NiCl
2.6H
2O:35-80g/L, H
3BO
3: 35-55g/L, nanometer additive: 5～60mL/L;
B) anode: sulfur-bearing nickel plate or nickel cake; C) negative electrode: Nd-Fe-B workpiece;
D) plating condition
Stir: pneumatic blending, pH:4.0-5.0, cathode current density: 2-5A/dm
2, temperature: 50-65 ℃;
2) electrolysis membrane removal
Voltage 4-6V, normal temperature, 30-60 second, catholyte, pure lead anode, electrolysis membrane removal in removing film;
The preparation method of described nanometer additive is: be the SiO of 10-100nm with granularity
2Nanoparticle and nonionogenic tenside mixing and ball milling, blending ratio is a nanoparticle: nonionogenic tenside=1: 0.5-10, then this mixture is mixed with cats product, water, blending ratio is a mixture: cats product: water=1: 0.2-3: 0.1-10 carries out batch mixing, strong shearing mechanism dispersed with stirring can obtain electroplating and use nanometer additive;
The described preparation method who removes film is: in concentration expressed in percentage by weight is in the saline solution of haloid element of 0.1%-20%, adds the sulfuric acid of 1-30%.
2. method according to claim 1 is characterized in that: described nanoparticle can also be nanometer ZrO
2Or Nano diamond or nano SiC, can add a kind of simultaneously or several nanoparticles.
3. method according to claim 1, it is characterized in that: described nonionogenic tenside is that structure is the A1-A2-A3-H type, wherein A1 is the alkyl of 8-18 carbon-chain structure, A2 is the structure of independent oxygen or the oxygen that links to each other with phenyl ring, A3 is the polymer-based group that contains oxyethyl group of 3-18 carbon-chain structure, and H is meant hydrogen atom.
4. method according to claim 1, it is characterized in that: described cats product is meant that structure is the B1-B2-B3-X-M type, wherein B1 is the alkyl group of 8-20 carbon-chain structure, B2 is the group of 1-3 methyl structural, B3 is benzyl or does not have group, X is a haloid element, and M is ammonium, sodium cation.
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|---|---|---|---|
| CN2005100321018A CN1924110B (en) | 2005-09-01 | 2005-09-01 | Metal based nano composite electric plating method for Nd-Fe-B material antisepsis |
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|---|---|---|---|
| CN2005100321018A CN1924110B (en) | 2005-09-01 | 2005-09-01 | Metal based nano composite electric plating method for Nd-Fe-B material antisepsis |
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| Publication Number | Publication Date |
|---|---|
| CN1924110A true CN1924110A (en) | 2007-03-07 |
| CN1924110B CN1924110B (en) | 2010-04-28 |
Family
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| US5286366A (en) * | 1991-11-05 | 1994-02-15 | Hitachi Magnetic Corp. | Surface treatment for iron-based permanent magnet including rare-earth element |
| JP2001257112A (en) * | 2000-03-14 | 2001-09-21 | Citizen Watch Co Ltd | Permanent magnet material |
| CN100348780C (en) * | 2004-03-16 | 2007-11-14 | 天津大学 | Method of pulse plating nickel based nano composite plating layer and equipment |
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