CN1410593A - Nickel phosphorus chemical plating method of neodymium iron boron permanent magnet material - Google Patents
Nickel phosphorus chemical plating method of neodymium iron boron permanent magnet material Download PDFInfo
- Publication number
- CN1410593A CN1410593A CN 01128227 CN01128227A CN1410593A CN 1410593 A CN1410593 A CN 1410593A CN 01128227 CN01128227 CN 01128227 CN 01128227 A CN01128227 A CN 01128227A CN 1410593 A CN1410593 A CN 1410593A
- Authority
- CN
- China
- Prior art keywords
- plating
- ultrasonic
- chemical
- oil removing
- follows
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 238000007747 plating Methods 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title claims abstract description 25
- 239000000126 substance Substances 0.000 title claims abstract description 24
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims description 18
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 title claims description 8
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 239000008139 complexing agent Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 230000004913 activation Effects 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006722 reduction reaction Methods 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims description 19
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 16
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 16
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- 230000002829 reductive effect Effects 0.000 claims description 13
- 150000002815 nickel Chemical class 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 239000001488 sodium phosphate Substances 0.000 claims description 11
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 11
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 11
- 238000007772 electroless plating Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000004471 Glycine Substances 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 229940046892 lead acetate Drugs 0.000 claims description 8
- 230000010355 oscillation Effects 0.000 claims description 8
- 235000019260 propionic acid Nutrition 0.000 claims description 8
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- 239000001384 succinic acid Substances 0.000 claims description 8
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 8
- 229940038773 trisodium citrate Drugs 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010431 corundum Substances 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 238000005137 deposition process Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 abstract 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000000536 complexating effect Effects 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 abstract 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 21
- 239000011159 matrix material Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 5
- 241000080590 Niso Species 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000003595 mist Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
In the invention, the sodium hypophosphite is as the reducing agent of the bath, nickel sulfate as the main salt, with the complexing agent, accelerating agent and stabilizing agent being added. The ultrasonic chemical plating and second chemical plating method are adopted that utilizes the mechanical energy of the ultrasonic vibration, making the bath deposit nickel and phosphor under the catalysis of the metal surafce and the chemical reduction method controlled. The plating procedure includes the steps of edge rounding, oil removal, rust removal, activation, chemical plating and post treatment. The multiple complexing, accelerating and stabilizing agents raises the stability of the bath. The plating speed is adjustable. The even, compact nickel and phosphor plating layer covers the surface of the base body of powder metallurgical material so as to increase the service life of the material and provide wide application area.
Description
Technical field
The present invention relates to field of chemical processing of material, specifically the chemical nickel and phosphor plating method of Nd-Fe-Bo permanent magnet material.
Background technology
The application of neodymium iron boron (NdFeB) permanent magnet material in recent years is very rapid with development, and is to be related to the key that can this material be applied to the protection success or not of Nd-Fe-Bo permanent magnet material.The NdFeB permanent magnet is the SmCo that continues
5And Sm
2Co
17Third generation rare earth permanent-magnetic material afterwards, owing to having higher saturation magnetization, coercive force and magnetic energy product, it becomes critical function material in the Modern High-Tech field, but because technological reason makes material surface have many micropores, the existence of the porous surface of NdFeB permanent magnet and rich neodymium phase, cause its easy oxidation and rusting, solidity to corrosion difference and its widespread use is restricted.
In the prior art, adopt technology such as the blunt method of Al-Cr acid, organic coat method, Vacuum Coating method, plating and electroless plating for the surface treatment of NdFeB material more, some effects have been obtained, still there is solidity to corrosion difference problem, as: the 32nd volume first phase of February calendar year 2001 " magneticsubstance and device " has been introduced the analysis of sintered Nd Fe B magnet plating defect, after electroplating processes, pit in irregular shape or hollow hole usually appear in magnets N i coating or some position of Zn coating, thereby influence the use of quality of coating and magnet; In addition, generally adopt chemical nickel plating coating or electro-coppering nickel composite deposite as protective layer at present in the world, wherein chemical nickel plating coating porosity is big, and anticorrosion effect is poor, and electroplates problems such as there being quality of coating instability in uneven thickness.
Summary of the invention
The purpose of this invention is to provide a kind of chemical nickel and phosphor plating method that makes material coating imporosity, thickness is even and solidity to corrosion is strong Nd-Fe-Bo permanent magnet material.
To achieve these goals, technical scheme of the present invention be plating bath with inferior sodium phosphate as reductive agent, single nickel salt is as main salt, additional complexing agent, accelerator, stablizer adopt ultrasonic electroless deposition technique and secondary chemical plating method, utilize the mechanical energy of ultrasonic oscillation, make plating bath under the katalysis of metallic surface, nickel phosphorus deposition process through the control chemical reduction method carries out comprises chamfering, oil removing, rust cleaning, activation, ultrasonic chemistry, electroless plating and post-processing step, and is specific as follows:
(1) chamfering
Adopt mechanical barreling chamfering method, be 1.0 by volume with NdFeB material and corundum sand: (1.0～1.5) are inserted in the airtight cylinder, and total amount accounts for 3/4 of total drum volume, add infiltrate submergence sample then; Start cylinder, drum rotational speed is 30～40r/min, and the time is 12～72 hours;
(2) oil removing
A. vacuum oil removing:
Adopt 120～200 ℃, 0.5～3 hour vacuum heat treatment;
B. alkali lye oil removing:
After the vacuum oil removing, carry out the alkali lye oil removing, alkali lye pH value is 8～10.5, the alkali lye prescription is as follows:
Na
2CO
3：5～20g/l；Na
3PO
4·12H
2O：10～30g/l；
Na
2SiO
3: 5～20g/l; OP-10 emulsifying agent: 1～5g/l;
Alkali liquid temperature is 60～80 ℃, adopts ultrasonic wave simultaneously, and ultrasonic frequency is that 19～80kHz, power are 50～500w, and the treatment time is 5～10 minutes;
(3) rust cleaning
Employing concentration is 5～40% HNO
3Carry out pickling, the time is 5～100 seconds;
(4) activation
Employing concentration is 1～10% H
2SO
4As activation solution, at room temperature soak time is: 5～50 seconds;
(5) ultrasonic chemistry
As reductive agent, single nickel salt is as main salt with inferior sodium phosphate for plating bath, and additional complexing agent, accelerator, stablizer adopt ultrasonic oscillation simultaneously, and the prescription of plating bath is as follows:
Main salt: single nickel salt NiSO
46H
2O:20～30g/l;
Reductive agent: inferior sodium phosphate NaH
2PO
2H
2O:30～40g/l;
Complexing agent: sodium acetate NaAC3H
2O:12～24g/l;
Propionic acid C
2H
5COOH:5～30g/l;
DL-oxysuccinic acid CHOHCH
2(COOH)
2: 5～30g/l;
Glycine NH
2CH
2COOH:1～10g/l;
EDTA?C
10H
16N
2O
8：1～10g/l；
Trisodium Citrate Na
3C
6H
5O
72H
2O:5～40g/l;
Accelerator: Succinic Acid (CH
2COOH)
2: 5～30g/l;
Stablizer: lead acetate (Pb
2+): 1～5ppm; Thiocarbamide H
2NCSNH
2: 0.5～5ppm;
The ultrasonic chemistry processing parameter is as follows:
Frequency 19～80kHz, power 50～500W, pH6.5～7.5,
70～85 ℃ of temperature, 1～15 minute time, plating speed is 10～60 μ m/ hours;
(6) electroless plating
The chemical plating bath prescription is as follows:
Main salt: single nickel salt NiSO
46H
2O:20～30g/l;
Reductive agent: inferior sodium phosphate NaH
2PO
2H
2O:30～40g/l;
Complexing agent: sodium acetate NaAC3H
2O:20～24g/l;
DL-oxysuccinic acid CHOHCH
2(COOH)
2: 5～25g/1;
Glycine NH
2CH
2COOH:1～10g/l;
Trisodium Citrate Na
3C
6H
5O
72H
2O:2～10g/l;
Lactic acid CH
3CHOHCOOH:5～25g/l;
Propionic acid C
2H
5COOH:5～25g/l;
Accelerator: Succinic Acid (CH
2COOH)
2: 5～25g/l;
Stablizer: lead acetate (Pb
2+): 1～5ppm; Thiocarbamide H
2NCSNH
2: 0.5～5ppm;
The chemical plating technology parameter is as follows:
Temperature: 86～90 ℃, ratio is loaded: 0.4～2 in pH:4.4～4.8
Loop cycle: 5～6, plating speed: 12～16 μ m/ hours;
(7) aftertreatment
Adopt CrO
3Carry out sealing of hole and handle processing parameter:
CrO
3: 1～10g/l, temperature: 70～85 ℃, time: 10～20 minutes;
Described infiltrate is: alcohol or water.
The principle of the invention: utilize the mechanical energy of ultrasonic oscillation to make plating bath produce many holes at the matrix table, these hole sustained oscillations produce powerful shock action to matrix surface, i.e. ultrasonic cavitation, ultrasonic cavitation can cause a large amount of activity freely to produce, make the matrix surface activation, quicken chemical reaction; Strengthen molecular impact on the other hand, make attached to the bubble in matrix surface and the hole and can in time discharge, thereby the nickel ion reduce deposition in the plating bath is had on the surface of catalytic activity, make that matrix surface plating one deck is even compact, imporous nickel-phosphorus coating, matrix is played protective effect.Then, in acidic bath, carry out the solidity to corrosion that the secondary electroless plating further improves coating, play protective effect better matrix.
Beneficial effect of the present invention is as follows:
1. coating imporosity and thickness are even, thereby have improved the corrosion resisting property of Nd-Fe-Bo permanent magnet material.The ni-p electroless plating prescription of the application of the invention development, adopt the sonochemistry electroplating method, utilize the mechanical energy of ultrasonic oscillation to make plating bath produce many holes at matrix surface, these holes produce powerful shock action to matrix surface, make the matrix surface activation, quicken chemical reaction, thereby, imporous nickel-phosphorus coating even compact at matrix surface plating one deck, then in acidic bath, carry out the solidity to corrosion that the secondary electroless plating further improves coating, play protective effect better matrix.
2. improve the work-ing life of Nd-Fe-Bo permanent magnet material, widen its Application Areas.When the nickel-phosphorus coating thickness that adopts the present invention to form at matrix surface reaches 30～40 microns, damp and hot, the High-Voltage Experimentation life-span is more than 500 hours, the salt mist experiment life-span is more than 300 hours, thereby make the Nd-Fe-Bo permanent magnet material range of application more extensive, can be applied to fields such as electronics, computer, automobile, medical treatment.
3. the present invention adopts multiple complexing agent and accelerator, stablizer, has improved bath stability, and plating speed can be regulated, and thickness of coating is even; Chemical plating method of the present invention is compared with plating, is easy to control, and electroplates owing to fringing effect, and current density is inhomogeneous, causes thickness of coating inhomogeneous.
4. the present invention can shorten the oil removing time by adopting vacuum oil removing and the oil removing of ultrasonic wave alkali lye, strengthens deoiling effect, improves processing quality.
5. to adopt concentration be 1～10% H in the present invention
2SO
4As activation solution, can remove the vaporization membrane as thin as a wafer on the specimen surface, and form uniform forming core active centre thereon, improve nickel plating phosphorus effect.
Embodiment
Be described in further detail the present invention below by embodiment.
Embodiment 1
Adopt the inventive method to carry out plating at neodymium-iron-boron permanent magnetic material surface, as follows operation successively:
(1) chamfering
Adopt mechanical barreling chamfering method, insert in the airtight ceramic roller by NdFeB material sample and 1.0: 1.0 amount of corundum sand volume ratio, total amount accounts for 3/4 of total drum volume, add alcohol submergence sample then, start cylinder, drum rotational speed is 30r/min, and the time is 36 hours;
(2) oil removing
A. vacuum oil removing:
Adopt 200 ℃, 1 hour vacuum heat treatment, remove the greasy dirt of NdFeB material surface, because the NdFeB permanent magnet is a mmaterial, surface irregularity, hole is many, and greasy dirt is had stronger adsorptive power, therefore adopts the vacuum oil removing; In addition, also can prevent the aerial oxidation of NdFeB permanent magnet;
B. alkali lye oil removing:
After the vacuum oil removing, carry out the alkali lye oil removing, alkali lye pH value is 10, the alkali lye prescription is as follows:
Na
2CO
3：15g/l；Na
3PO
4·12H
2O：20g/l；
Na
2SiO
3: 5g/l; OP-10 emulsifying agent: 1g/l
(OP-10 emulsifying agent, commercially available prod, source: reagent shop, Shenyang)
Alkali liquid temperature is 60 ℃, adopts ultrasonic wave simultaneously, and ultrasonic frequency is that 19kHz, power are 200w, and the treatment time is 5 minutes;
In order to guarantee the bonding strength of NdFeB permanent magnet surfaces coating, after the vacuum oil removing, also should carry out the alkali lye oil removing; Because NdFeB is very active, therefore, the alkalescence of design alkaline solution should not be too strong, and the pH value is not more than 10.5; In addition, in order to improve deoiling effect, adopt ultrasonic wave simultaneously, ultrasonic wave can be strengthened the oil removing process, shortens the oil removing time, improves processing quality;
(3) rust cleaning
Employing concentration is 20% HNO
3Carry out pickling, the time is 30 seconds; Because the very easily oxidation of NdFeB material needs before the plating to remove the table zone of oxidation, magnet is the silver gray surface cleaning after the pickling;
(4) activation
Employing concentration is 10% H
2SO
4As activation solution, at room temperature soak time is 15 seconds.In order to remove the vaporization membrane as thin as a wafer on the specimen surface, and the uniform forming core of shape active centre thereon, before carrying out electroless plating, carry out activation treatment;
(5) ultrasonic chemistry
As reductive agent, single nickel salt is as main salt with inferior sodium phosphate for plating bath, and additional complexing agent, accelerator, stablizer adopt ultrasonic oscillation simultaneously, and the prescription of plating bath is as follows:
Main salt: NiSO
46H
2O:27g/l;
Reductive agent: NaH
2PO
2H
2O:33g/l;
Complexing agent: NaAC3H
2O:12g/l; Propionic acid: 6g/l; DL-oxysuccinic acid: 8g/l;
Glycine: 2g/l; EDTA:2g/l; Trisodium Citrate: 15g/l;
Accelerator: Succinic Acid: 10g/l;
Stablizer: lead acetate (Pb
2+) 1ppm; Thiocarbamide: 1ppm;
Processing parameter: frequency 20kHz, power 200W, pH6.5,70 ℃ of temperature, were plated fast 40 μ m/ hours at 10 minutes time; Various ions violent random encounters under the effect of ultrasonic wave field under the katalysis of metallic surface, is carried out nickel phosphorus deposition through the control chemical reduction method in the plating bath, can plate evenly complete coating of one deck, and outward appearance is silvery white in color and coating is combined;
(6) electroless plating
The chemical plating bath prescription is as follows:
Main salt: NiSO
46H
2O:27g/l;
Reductive agent: NaH
2PO
2H
2O:30g/l;
Complexing agent: NaAC3H
2O:20g/l; DL-oxysuccinic acid: 12g/l; Glycine: 1g/l;
Trisodium Citrate: 2g/l; Lactic acid: 10g/l; Propionic acid: 10g/l;
Accelerator: Succinic Acid: 16g/l;
Stablizer: lead acetate: 2ppm; Thiocarbamide: 2ppm;
The chemical plating technology parameter is as follows:
Temperature: 86 ℃, 2.5 hours time, pH:4.6, loading ratio: 1, loop cycle: 5, plating speed: 12 μ m/ hours; Various ions are under the katalysis of metallic surface, through controlling the nickel phosphorus deposition process that chemical reduction method carries out in the plating bath;
(7) aftertreatment
Adopt CrO
3Carry out sealing of hole and handle processing parameter:
CrO
3: 3g/l, temperature: 78 ℃, time: 15 minutes;
Through above-mentioned processing, obtaining thickness of coating is 30 microns.
Embodiment 2
Difference from Example 1 is:
The ultrasonic chemistry prescription is as follows:
Main salt: single nickel salt: 30g/l;
Reductive agent: inferior sodium phosphate: 40g/l;
Complexing agent: sodium acetate: 24g/l; Propionic acid: 20g/l; DL-oxysuccinic acid: 20g/l;
Glycine: 6g/l; EDTA:5g/l; Trisodium Citrate: 20g/l;
Accelerator: Succinic Acid: 20g/l;
Stablizer: lead acetate (Pb
2+): 2ppm; Thiocarbamide H
2NCSNH
2: 3ppm;
The ultrasonic chemistry processing parameter is as follows:
Frequency: 80kHz, power: 500W, pH:7.0, temperature: 85 ℃, time: 2 minutes, the plating fast 30 μ m/ hours;
The chemical plating bath prescription is as follows:
Main salt: single nickel salt: 30g/l;
Reductive agent: inferior sodium phosphate: 40g/l;
Complexing agent: sodium acetate: 24g/l; DL-oxysuccinic acid: 20g/l; Glycine: 5g/l;
Trisodium Citrate: 6g/l; Lactic acid: 15g/l; Propionic acid: 15g/l;
Accelerator: Succinic Acid: 25g/l;
Stablizer: lead acetate (Pb
2+): 5ppm; Thiocarbamide: 5ppm;
The chemical plating technology parameter is as follows:
Temperature: 90 ℃, the time: 2.5 hours, pH:4.8, load ratio: 2,
Loop cycle: 6, plating speed: 16 μ m/ hours;
The aftertreatment technology parameter:
CrO
3: 6g/l, temperature: 82 ℃, time: 20 minutes.
Through above-mentioned processing, obtaining thickness of coating is 40 microns.
Relevant comparative example
Employing the present invention prepares the protective coating of NdFeB material and the corrosion resisting property of relevant chemical plating method compares, and is as shown in table 1:
Table 1
| Chemical plating method | Salt mist experiment | Porosity | Damp and hot experiment | High-Voltage Experimentation |
| Acidic bath: can't plating | ||||
| Alkali plating solution (30 microns) | 24 hours | 2％ | 72 hours | 48 hours |
| Neutral plating bath (30 microns) | 120 hours | 1％ | 240 hours | 226 hours |
| The present invention's (30 microns) | ＞300 hours | Do not have | ＞500 hours | ＞500 hours |
Found out by table 1, because neodymium iron boron is mmaterial, can't carry out plating in common acidic bath, though can plate in alkali plating solution, coating stress is big, poor adhesive force and porosity are big, and edge begins to come off when salt mist experiment.
Claims (2)
1. the chemical nickel and phosphor plating method of a Nd-Fe-Bo permanent magnet material, it is characterized in that: plating bath with inferior sodium phosphate as reductive agent, single nickel salt is as main salt, additional complexing agent, accelerator, stablizer, adopt ultrasonic electroless deposition technique and secondary chemical plating method, utilize the mechanical energy of ultrasonic oscillation, make plating bath under the katalysis of metallic surface, carry out nickel phosphorus deposition process through the control chemical reduction method, comprise chamfering, oil removing, rust cleaning, activation, ultrasonic chemistry, electroless plating and post-processing step, specific as follows:
1) chamfering
Adopt mechanical barreling chamfering method, be 1.0 by volume with NdFeB material and corundum sand: (1.0～1.5) are inserted in the airtight cylinder, and total amount accounts for 3/4 of total drum volume, add infiltrate submergence sample then; Start cylinder, drum rotational speed is 30～40r/min, and the time is 12～72 hours;
2) oil removing
A. vacuum oil removing:
Adopt 120～200 ℃, 0.5～3 hour vacuum heat treatment;
B. alkali lye oil removing:
After the vacuum oil removing, carry out the alkali lye oil removing, alkali lye pH value is 8～10.5, the alkali lye prescription is as follows:
Na
2CO
3：5～20g/l；Na
3PO
4·12H
2O：10～30g/l；
Na
2SiO
3: 5～20g/l; OP-10 emulsifying agent: 1～5g/l;
Alkali liquid temperature is 60～80 ℃, adopts ultrasonic wave simultaneously, and ultrasonic frequency is that 19～80kHz, power are 50～500w, and the treatment time is 5～10 minutes;
3) rust cleaning
Employing concentration is 5～40% HNO
3Carry out pickling, the time is 5～100 seconds;
4) activation
Employing concentration is 1～10% H
2SO
4As activation solution, at room temperature soak time is: 5～50 seconds;
5) ultrasonic chemistry
As reductive agent, single nickel salt is as main salt with inferior sodium phosphate for plating bath, and additional complexing agent, accelerator, stablizer adopt ultrasonic oscillation simultaneously, and the prescription of plating bath is as follows:
Main salt: single nickel salt: 20～30g/l; Reductive agent: inferior sodium phosphate: 30～40g/l;
Complexing agent: sodium acetate: 12～24g/l; Propionic acid: 5～30g/l; DL-oxysuccinic acid: 5～30g/l;
Glycine: 1～10g/l; EDTA:1～10g/l; Trisodium Citrate: 5～40g/l;
Accelerator: Succinic Acid: 5～30g/l; Stablizer: lead acetate: 1～5ppm, thiocarbamide: 0.5～5ppm;
The ultrasonic chemistry processing parameter is as follows:
Frequency 19～80kHz, power 50～500W, pH6.5～7.5,70～85 ℃ of temperature,
1～15 minute time, plating speed is 10～60 μ m/ hours;
6) electroless plating
The chemical plating bath prescription is as follows:
Main salt: single nickel salt: 20～30g/l; Reductive agent: inferior sodium phosphate: 30～40g/l;
Complexing agent: sodium acetate: 20～24g/l; DL-oxysuccinic acid: 5～25g/l; Glycine: 1～10g/l;
Trisodium Citrate: 2～10g/l; Lactic acid: 5～25g/l; Propionic acid: 5～25g/l;
Accelerator: Succinic Acid: 5～25g/l; Stablizer: lead acetate: 1～5ppm; Thiocarbamide: 0.5～5ppm;
The chemical plating technology parameter is as follows:
Temperature: 86～90 ℃, pH:4.4～4.8, load ratio: 0.4～2,
Loop cycle: 5～6, plating speed: 12～16 μ m/ hours;
7) aftertreatment
Adopt CrO
3Carry out sealing of hole and handle processing parameter:
CrO
3: 1～10g/l, temperature: 70～85 ℃, time: 10～20 minutes.
2. according to the chemical nickel and phosphor plating method of the described Nd-Fe-Bo permanent magnet material of claim 1, it is characterized in that: the described infiltrate of step 1 is: alcohol or water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011282274A CN1150350C (en) | 2001-09-29 | 2001-09-29 | Nickel phosphorus chemical plating method of neodymium iron boron permanent magnet material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011282274A CN1150350C (en) | 2001-09-29 | 2001-09-29 | Nickel phosphorus chemical plating method of neodymium iron boron permanent magnet material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1410593A true CN1410593A (en) | 2003-04-16 |
| CN1150350C CN1150350C (en) | 2004-05-19 |
Family
ID=4668109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011282274A Expired - Fee Related CN1150350C (en) | 2001-09-29 | 2001-09-29 | Nickel phosphorus chemical plating method of neodymium iron boron permanent magnet material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1150350C (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402698C (en) * | 2006-01-26 | 2008-07-16 | 鲁国强 | Electroless nickel-phosphorus plating process for Nd-Fe-Bo permanent magnet material |
| CN101586236A (en) * | 2009-06-30 | 2009-11-25 | 奇瑞汽车股份有限公司 | Stable chemical nickel-plating plating solution and preparation method thereof |
| CN102040947A (en) * | 2009-10-13 | 2011-05-04 | 北京中科三环高技术股份有限公司 | Biological oil removing agent for permanent-magnet materials |
| CN102041488A (en) * | 2009-10-14 | 2011-05-04 | 三环瓦克华（北京）磁性器件有限公司 | Pre-plating process of chemically-plated Ni-P alloy |
| CN101372740B (en) * | 2007-08-23 | 2011-05-11 | 北京中科三环高技术股份有限公司 | Copper plating bath for coating copper and method for surface copper plating permanent magnetic material using the same |
| CN101373651B (en) * | 2007-08-23 | 2011-12-07 | 北京中科三环高技术股份有限公司 | Surface pretreating method of wet method spray sand type neodymium iron boron permanent magnetic material |
| CN102400118A (en) * | 2011-11-18 | 2012-04-04 | 钢铁研究总院 | Preparation method of nickel phosphorus alloy plating on surface of sintered neodymium iron boron permanent magnet |
| CN102534697A (en) * | 2011-12-08 | 2012-07-04 | 中国科学院金属研究所 | Nickel plating/organic coating double-layer surface protection method for NdFeB (neodymium-iron-boron) magnet material |
| CN102732871A (en) * | 2011-04-15 | 2012-10-17 | 中国科学院金属研究所 | Neodymium iron boron magnet material phosphating treatment and organic coating double layers protection method |
| CN103305819A (en) * | 2012-03-16 | 2013-09-18 | 中国石油化工集团公司 | Chemical plating solution of oilfield drilling tool and anti-corrosion protection method of drilling tool |
| CN103451663A (en) * | 2013-08-19 | 2013-12-18 | 南通保来利轴承有限公司 | Method for treating surface of rare earth permanent magnetic material |
| CN104032342A (en) * | 2014-06-11 | 2014-09-10 | 安徽大地熊新材料股份有限公司 | Method for improving combining force of sintered Nd-Fe-B magnet and electroplated coating |
| CN105369226A (en) * | 2015-12-07 | 2016-03-02 | 湖南航天磁电有限责任公司 | Chemical nickel phosphor plating solution for surface acidity of sintered NdFeB magnet, and nickel phosphor plating process |
| CN105420703A (en) * | 2015-12-18 | 2016-03-23 | 中国钢研科技集团有限公司 | Ultrasonic chemical nickel and phosphorus plating method for NdFeB material |
| CN108109834A (en) * | 2017-12-20 | 2018-06-01 | 宁波市鄞州智伴信息科技有限公司 | Strong permanent magnetism material formula of a kind of corrosion resistance and preparation method thereof |
| CN116140157A (en) * | 2023-02-23 | 2023-05-23 | 合肥工业大学 | Surface spraying method for bonded NdFeB magnet |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427642C (en) * | 2006-05-11 | 2008-10-22 | 浙江大学 | Method of raising binding force of chemical coating on the surface of NdFeB permanent magnet |
-
2001
- 2001-09-29 CN CNB011282274A patent/CN1150350C/en not_active Expired - Fee Related
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402698C (en) * | 2006-01-26 | 2008-07-16 | 鲁国强 | Electroless nickel-phosphorus plating process for Nd-Fe-Bo permanent magnet material |
| CN101372740B (en) * | 2007-08-23 | 2011-05-11 | 北京中科三环高技术股份有限公司 | Copper plating bath for coating copper and method for surface copper plating permanent magnetic material using the same |
| CN101373651B (en) * | 2007-08-23 | 2011-12-07 | 北京中科三环高技术股份有限公司 | Surface pretreating method of wet method spray sand type neodymium iron boron permanent magnetic material |
| CN101586236A (en) * | 2009-06-30 | 2009-11-25 | 奇瑞汽车股份有限公司 | Stable chemical nickel-plating plating solution and preparation method thereof |
| CN102040947A (en) * | 2009-10-13 | 2011-05-04 | 北京中科三环高技术股份有限公司 | Biological oil removing agent for permanent-magnet materials |
| CN102040947B (en) * | 2009-10-13 | 2014-03-26 | 北京中科三环高技术股份有限公司 | Biological oil removing agent for permanent-magnet materials |
| CN102041488A (en) * | 2009-10-14 | 2011-05-04 | 三环瓦克华（北京）磁性器件有限公司 | Pre-plating process of chemically-plated Ni-P alloy |
| CN102732871A (en) * | 2011-04-15 | 2012-10-17 | 中国科学院金属研究所 | Neodymium iron boron magnet material phosphating treatment and organic coating double layers protection method |
| CN102400118A (en) * | 2011-11-18 | 2012-04-04 | 钢铁研究总院 | Preparation method of nickel phosphorus alloy plating on surface of sintered neodymium iron boron permanent magnet |
| CN102534697A (en) * | 2011-12-08 | 2012-07-04 | 中国科学院金属研究所 | Nickel plating/organic coating double-layer surface protection method for NdFeB (neodymium-iron-boron) magnet material |
| CN102534697B (en) * | 2011-12-08 | 2014-10-29 | 中国科学院金属研究所 | Nickel plating/organic coating double-layer surface protection method for NdFeB (neodymium-iron-boron) magnet material |
| CN103305819A (en) * | 2012-03-16 | 2013-09-18 | 中国石油化工集团公司 | Chemical plating solution of oilfield drilling tool and anti-corrosion protection method of drilling tool |
| CN103305819B (en) * | 2012-03-16 | 2016-04-27 | 中国石油化工集团公司 | A kind of oil field tool chemical plating fluid and drilling tool corrosionproof protection method |
| CN103451663A (en) * | 2013-08-19 | 2013-12-18 | 南通保来利轴承有限公司 | Method for treating surface of rare earth permanent magnetic material |
| CN103451663B (en) * | 2013-08-19 | 2015-09-02 | 南通保来利轴承有限公司 | A kind of method of surface of rare earth permanent-magnetic process |
| CN104032342A (en) * | 2014-06-11 | 2014-09-10 | 安徽大地熊新材料股份有限公司 | Method for improving combining force of sintered Nd-Fe-B magnet and electroplated coating |
| CN104032342B (en) * | 2014-06-11 | 2016-09-14 | 安徽大地熊新材料股份有限公司 | A kind of method improving Sintered NdFeB magnet and electrodeposited coating adhesion |
| CN105369226A (en) * | 2015-12-07 | 2016-03-02 | 湖南航天磁电有限责任公司 | Chemical nickel phosphor plating solution for surface acidity of sintered NdFeB magnet, and nickel phosphor plating process |
| CN105420703A (en) * | 2015-12-18 | 2016-03-23 | 中国钢研科技集团有限公司 | Ultrasonic chemical nickel and phosphorus plating method for NdFeB material |
| CN108109834A (en) * | 2017-12-20 | 2018-06-01 | 宁波市鄞州智伴信息科技有限公司 | Strong permanent magnetism material formula of a kind of corrosion resistance and preparation method thereof |
| CN116140157A (en) * | 2023-02-23 | 2023-05-23 | 合肥工业大学 | Surface spraying method for bonded NdFeB magnet |
| CN116140157B (en) * | 2023-02-23 | 2023-10-13 | 合肥工业大学 | Surface spraying method for bonded NdFeB magnet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1150350C (en) | 2004-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1150350C (en) | Nickel phosphorus chemical plating method of neodymium iron boron permanent magnet material | |
| CN1150349C (en) | Method of supersonic chemical plating nickel phosphorus of powder metallurgy material | |
| CN1807682A (en) | Electroless nickel-phosphorus plating process for Nd-Fe-Bo permanent magnet material | |
| CN1299300C (en) | Rare earth element sintered magnet and method for producing rare earth element sintered magnet | |
| CN1309862C (en) | Nonelectrolytic gold plating liquid and method thereof | |
| CN1387745A (en) | Copper foil excellent in laser beam drilling performance and production method therefor | |
| CN1500916A (en) | Gradient composite deposite for continuous casting crystallizer copper plate and production method thereof | |
| CN104805413A (en) | Method for preparing surface coating of NdFeB permanent-magnet material | |
| CN1955343A (en) | Electroplating method of alluminium alloy surface | |
| CN101033550A (en) | Micro-corrosion liquid and application thereof in printing wiring board silver aggradation pretreatment | |
| CN1386146A (en) | Electrolytic copper-plated R-T-B magnet and method thereof | |
| CN101372740B (en) | Copper plating bath for coating copper and method for surface copper plating permanent magnetic material using the same | |
| CN111321436B (en) | Cyanide-free copper plating solution assistant and copper plating solution | |
| CN1843997A (en) | Method of plating on a glass base plate, a disk substrate, method for manufacturing the same and a perpendicular magnetic recording medium | |
| CN1873058A (en) | Plating solution, conductive material, and surface treatment method of conductive material | |
| CN1265028C (en) | Method for forming electroplated coating on surface of article | |
| CN1205626C (en) | High corrosion-resistant R-Fe-B-base bonded magnet and method of manufacturing the same | |
| JP2005523584A5 (en) | ||
| CN106862740B (en) | Preparation method of sintered NdFeB surface coating with high corrosion resistance and high binding force | |
| CN117702205A (en) | Nickel-cobalt-tungsten alloy electrodeposition solution for electroplating sintered neodymium-iron-boron permanent magnet and application thereof | |
| CN104419958A (en) | Neodymium iron boron permanent magnet material low magnetic reducing electroplating method | |
| CN1029995C (en) | Wear-resistant coating for titanium-base material | |
| CN116065208A (en) | Preparation method of variable-frequency power ultrasonic electro-deposition nano nickel-based composite layer on magnesium alloy surface | |
| CN111101173A (en) | Multilayer nickel plating and dehydrogenation process for neodymium iron boron permanent magnet material | |
| CN1215492C (en) | Technolgy for closing moulded product pore and adhesive mangetic body for closing pore using the technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |