The preparation method of nickel phosphorus alloy plating on surface of sintered neodymium iron boron permanent magnet
Technical field
The present invention relates to the preparation method in metal material surface chemical treatment field, particularly a kind of corrosion resistant chemical nickeling phosphorus alloy film.
Background technology
Sintered Nd-Fe-B permanent magnet has the title of " magnetic king ", it has higher coercive force, the specific magnetising moment and magnetic energy product, but also having the advantages such as energy consumption is low, density is little, physical strength is high, magnetic loss is low, Nd-Fe-B permanent magnet can be widely used in the fields such as electric motor, nuclear magnetic resonance, computer, magnetic separation.But Curie temperature and the working temperature of Nd-Fe-B permanent magnet are lower, and it is easily oxidized and corrosion in surrounding medium, thereby has caused its magnetic property sharply to descend, thereby has limited its application.
Intergranular corrosion is Nd-Fe-B permanent magnet main forms of corrosion under damp and hot environment, and the corrosion process of " phase selectivity " is the typical corrosion process of magnet, rich neodymium at first corrosion, then principal phase Nd mutually in magnet alloy
2Fe
14General corrosion occurs in B mutually then, and rich neodymium phased soln makes the disappearance of the crystal boundary between main phase grain in alloy, causes main phase grain to come off.In addition, due to each corrosion potential difference in corrosive medium of magnet, thereby the rich neodymium phase in magnet and the boron-rich phase anode that becomes corrosion cell, and principal phase Nd
2Fe
14B becomes the negative electrode of corrosion cell mutually, has formed " large negative electrode, primary anode " corrosion microbattery configurations, has aggravated the galvanic corrosion of magnet.Sintered Nd-Fe-B permanent magnet corrodibility is poor has restricted its application in the every profession and trade field, takes suitable measure to slow down and eliminates its corrosion, has become to be badly in need of the problem that solves.
So far, aspect the research of Nd-Fe-B permanent magnet corrosion and protection, carried out many work, as oxidation, the interpolation alloying element that alleviates powder in pulverizing process as far as possible, and coating coating protection etc. has been carried out on the surface of block magnet.The energy of oxidation that slows down powder improves magnet performance preferably, but can have higher requirement to flouring technology; Though add the solidity to corrosion that alloying element can improve magnet, tend to change the microstructure of crystal, weaken the performance of Nd-Fe-B permanent magnet, alloying can not fundamentally solve the corrosion difficult problem of magnet.
At present, the method for external coating protective coating is mainly taked in the protection of sintered Nd-Fe-B permanent magnet, namely stops air, water and other corrosivess to the magnet internal penetration by coating or coating, to improve the corrosion resistance of magnet.The protective coating that is used for sintered Nd-Fe-B permanent magnet mainly contains metal plating, polymeric coating and compound coating etc.Adopt plating, electroless plating or physical vaporous deposition with metals such as Ni, Cr, Zn, the metal plating plating such as Ni-P, TiN can play the effect of protection magnet in the sintered Nd-Fe-B permanent magnet surface.Electronickelling technique can access thicker protective coating, and its cost is relatively cheap, but also there is self-defect in this technology, and as there being the corner effect in the plating process, on plating piece, the each several part thickness of coating is uneven, plating defect is more, and the coating porosity is larger; Galvanizing technique has advantages of that cost is low, technique is simple, produce and easily control, and usually all can consider under envrionment conditions to use, but its coating can significantly descend when using under severe environment in the life-span; Chemical nickel plating has good barrier propterty, and is specially adapted to the member of complex construction.The using polymer protective coating can be realized under more serious corrosive environment the effective protection to magnet.When applied environment required magnet surface is carried out electrical isolation, polymeric coating was also more satisfactory selection.The material that is used for Nd-Fe-B permanent magnet rot-resistant polymeric coating is mainly resene, as epoxy resin.In some cases, need Nd-Fe-B permanent magnet to work in rugged environment, at this moment single coating can not satisfy the requirement of shelter to magnet, can consider to adopt two or more coating, forms many protection systems in magnet surface.But above technology can not realize the long-term protection to sintered Nd-Fe-B permanent magnet.
In numerous corrosion protection coatings, the Ni-P chemical plating has good erosion resistance, be widely used in the anticorrosion research of various metals material, chemical plating nickel-phosphorus alloy is because the solidity to corrosion of excellence is widely used in various industrial environments, but the different alloy layer solidity to corrosion in different corrosive mediums and environment of phosphorus content has obvious difference, decide according to concrete application conditions.Generally, the solidity to corrosion of Ni-P coating in Oxidant is relatively poor, and the corrosion resisting property of long period of soaking in sodium chloride solution is also undesirable, thereby take the Ni-P protective coating as matrix, it is carried out modification, research and develop the modification nickel-phosphorus coating novel, that corrosion resisting property is good significant.As with nickel-phosphorus coating CrO
3Solution carries out Passivation Treatment, can improve its salt spray corrosion resistance; Adopt dual nickel-phosphorus coating, be about to High phosphorus alloys coating and low phosphor alloy coating effectively compound, can effectively improve the corrosion resisting property of nickel-phosphorus coating; The elements such as doped with Cu, Zn, W, Cr and Re, can obtain the good nickel phosphorus multi-element layers of corrosion resisting property in nickel-phosphorus coating; Adopt chemical nickel phosphorus plating and various inert particulate codeposition, can obtain the brand-new composite deposite of function, as Ni-P-Al
2O
3﹑ Ni-P-SiC ﹑ Ni-P-Cr
2O
3The composite deposites such as ﹑ Ni-P-PTFE, Ni-P-PVDF, Ni-P-graphite, thereby solidity to corrosion, wear resistance and the lubricity of raising nickel-phosphorus alloy coating.
Chemical nickeling phosphorus alloy film belongs to galvanic protection coating to most of alloy materials, guarantee that nickel-phosphorus coating has good corrosion resisting property, must make it form complete blocking layer on metal alloy surface.The corrosion of nickel-phosphorus coating mainly contains two kinds of forms, and a kind of is uniform corrosion, and another kind is in the place's generation spot corrosion of coating hole.If nickel-phosphorus coating exists hole or defective will have a strong impact on the protection effect of coating.
Chlorion is aggressiveness ion main in water surrounding, and it easily permeates to metallic matrix by the protective coating surface, when itself and protected metallic contact, usually can cause spot corrosion, crevice corrosion and the intergranular corrosion of metallic substance.From the application of the corrosion prevention of nickel-phosphorus alloy coating, its protection against corrosion emphasis should be the local corrosion that chlorion causes.At present, great majority research is still implemented the nickel-phosphorus coating sealing of hole and is processed or adopt nickel phosphorus multi-elements alloying coating and nickel-phosphorus composite deposit, suppress the destruction of aggressiveness chlorion to alloyed metals such as sintered Nd-Fe-B permanent magnets in corrosive medium by the mechanical barrier effect, fundamentally do not eliminate chlorion to the harm of sintered Nd-Fe-B permanent magnet, finally limited the application of sintered Nd-Fe-B permanent magnet in each field.
To fundamentally eliminate the harm that chlorion exists metallic substance such as sintered Nd-Fe-B permanent magnets, should stop it to permeate to the metallic surface migration by nickel-phosphorus coating, if have the functional group of sulfonic acid of cation selective penetrating quality at the nickel-phosphorus alloy coating surface grafting, the selection infiltration of chlorion will be suppressed, stop chlorion to permeate to metal material matrix is surperficial by nickel-phosphorus alloy coating, thereby eliminated the potential hazard of chlorion, effectively improved the antiseptic property of nickel-phosphorus alloy coating.Have research report to adopt gamma-ray irradiation/Chemical Grafting Technique, grafting sulfonic acid and carboxylic-acid functional group in the Ni-P-PTFE composite deposite suppress chlorion to the coating internal penetration, thus effective corrosion resisting property that improves the carbon steel metal material.If adopt this technology to have sulfonic acid or the carboxylic-acid functional group of cation selective penetrating quality at the sintered Nd-Fe-B permanent magnet surface grafting, gamma-ray irradiation can have a negative impact to the magnetic property of Sintered NdFeB magnet, and chemical graft efficient is lower.
Summary of the invention
For overcoming the deficiencies in the prior art, effectively improve the performance that the nickel phosphorus alloy plating on surface of sintered neodymium iron boron permanent magnet anti-chlorine ion corrodes, the invention provides a kind of preparation method of nickel phosphorus alloy plating on surface of sintered neodymium iron boron permanent magnet, by the chemical modification technique to nickel-phosphorus alloy coating, can effectively suppress with the slowing down corrosion medium in chlorion by nickel-phosphorus alloy coating to surface of Nd-Fe-B permanent magnet migration infiltration, effectively avoid the generation of magnet local corrosion, improve nickel-phosphorus alloy coating to the barrier propterty of sintered Nd-Fe-B permanent magnet.
To achieve these goals, the invention provides following technical scheme:
A kind of preparation method of nickel phosphorus alloy plating on surface of sintered neodymium iron boron permanent magnet wherein, comprises the steps:
1) pre-treatment is carried out on the sintered Nd-Fe-B permanent magnet surface;
2) at the nickel-phosphorus alloy coating of sintered Nd-Fe-B permanent magnet surface employing chemically plating for surface doping polyvinylidene difluoride (PVDF) particulate;
3) to above-mentioned chemical nickeling phosphorus alloy film, adopt solution alkalization/thermal induction Chemical Grafting Technique to carry out modification, make and be grafted with the diactinic functional group of sulfonic acid of cation selective in nickel-phosphorus alloy coating.
The chemical modification reagent that uses in described step 3) comprises 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid, acrylamide, methylene-bisacrylamide and ammonium persulphate.
The process for preparation that is used for the chemical modification liquid that the grafting modification of described step 3) chemical nickeling phosphorus alloy film adopts is:
A. the concentration of each reagent is: 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid 80~120g/L, acrylamide 4~7g/L, methylene-bisacrylamide 5~8g/L, ammonium persulphate 4~6g/L;
B. solvent for use is deionized water or distilled water;
C. being formulated in air of chemical modification liquid carried out;
D. the addition sequence of each reagent is: 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid, acrylamide, methylene-bisacrylamide, ammonium persulphate;
In the process for preparation of wherein said chemical modification liquid, solution temperature is no more than 50 ℃.
The step that adopts solution alkalization/thermal induction Chemical Grafting Technique to prepare 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid modified chemical plating nickel-phosphorus alloy coating in described step 3) is:
A. with step 2) in the nickel-phosphorus alloy coating of surface doping polyvinylidene difluoride (PVDF) particulate of Sintered NdFeB magnet surface preparation be immersed in the sodium hydroxide solution that concentration is 80g/L, soaking at room temperature 15min, make in described coating the polyvinylidene difluoride (PVDF) microparticle surfaces have carbon-carbon double bond to generate, after 15min with its taking-up and clean up with deionized water;
B. the described nickel-phosphorus alloy coating that cleans up in step a is dipped in chemical modification liquid, soak time is 15~30min;
C. the described nickel-phosphorus alloy coating after processing through step b takes out from chemical modification liquid, remove the unnecessary solution in its surface, be placed in well heater and heat-treat, keep 80 ℃~120 ℃ of temperature, heat treatment time is 20~30min, and thermal treatment is carried out in air;
D. after thermal treatment finished, at first the described nickel-phosphorus alloy coating after processing through step c used 95% ethanolic soln soaking at room temperature 30min, then rinses well with deionized water, dries at 80 ℃~120 ℃ temperature at last.
The pretreated step on described step 1) sintered Nd-Fe-B permanent magnet surface is:
A. surface finish: with the sand paper of 40#, 80#, 300#, polished in the sintered Nd-Fe-B permanent magnet surface at first successively, and then adopt successively 600#, 800# and 1000# waterproof abrasive paper to carry out fine grinding to magnet surface, and clean up with deionized water, make its surface clean, smooth, smooth;
B. surface-sealing: at first in deionized water, sintered Nd-Fe-B permanent magnet is boiled 5min, then magnet is placed in ultrasound bath and processes 1min, remove its surperficial metal fragment and other impurity;
C. surface degreasing: the oil removing solution composition is: sodium phosphate 70g/L, and sodium carbonate 50g/L, sodium hydroxide 10g/L, degreasing fluid pH value adopts acetic acid to be adjusted into 9~10; The degreasing fluid temperature is controlled to be 65 ℃, and the auxiliary oil removing time of ultrasonic wave is 3min; At first sintered Nd-Fe-B permanent magnet after oil removing adopts 55 ℃~65 ℃ hot water to carry out the auxiliary cleaning of ultrasonic wave, and then adopts flowing cool water to rinse, and guarantees the not residual any degreasing fluid in its surface;
D. surface active: activation solution consist of nitric acid 120g/L, urea 10g/L, activation temperature is 25 ℃, soak time is 45s; At first sintered Nd-Fe-B permanent magnet after activation adopts 55 ℃~65 ℃ hot water to clean, and then adopts flowing cool water to rinse, and guarantees the not residual any activation solution in its surface;
E. zinc-nickel is soaked on the surface: soaking the zinc-nickel solution composition is: basic nickel carbonate 4g/L, and zinc oxide 8g/L, hydrofluoric acid 80g/L soaks the zinc-nickel time to be controlled to be 60s;
F. surface reduction: sintered Nd-Fe-B permanent magnet is taken out from soaking zinc-nickel solution, the sodium hypophosphite solution that is placed in immediately concentration and is 20g/L is reduced, make the sintered Nd-Fe-B permanent magnet surface deposition have zinc, the nickel fine particle of catalytic activity, reduction temperature is room temperature, and the recovery time is 60s.
Described step 2) in the standby nickel-phosphorus alloy coating of surface doping polyvinylidene difluoride (PVDF) particulate of sintered Nd-Fe-B permanent magnet surface employing chemically plating, comprise the steps:
A. the preparation of chemical plating fluid:
Consisting of of chemical plating fluid: single nickel salt 20~30g/L, sodium hypophosphite 20~35g/L, lactic acid 10~20g/L, citric acid 5~8g/L, sodium acetate 4~8g/L, succinic acid 4~6g/L, ammonium bifluoride 3~7g/L, Potassium Iodate 8~12mg/L, fluorine carbon type cats product 0.3~0.6g/L, polyvinylidene difluoride (PVDF) particle 4~7g/L, the particle diameter of polyvinylidene difluoride (PVDF) particle are 0.5~5 μ m;
At first in deionized water, single nickel salt, sodium hypophosphite, lactic acid, citric acid, sodium acetate, succinic acid, ammonium bifluoride, Potassium Iodate dissolving are mixed, pH value with ammoniacal liquor adjustment solution is 4.6~5.2 again, then with fluorine carbon type cats product anhydrous alcohol solution, and mix with the polyvinylidene difluoride (PVDF) particulate, after fully stirring, it is slowly joined in above-mentioned plating solution and fully stir, then make bath temperature slowly be increased to 85 ℃~90 ℃;
B. at first will be positioned over through the sintered Nd-Fe-B permanent magnet that step 1) was processed above-mentioned steps and a) carry out plating in prepared plating solution, keeping bath temperature is 85 ℃~90 ℃, after 90min, sintered Nd-Fe-B permanent magnet is taken out from plating solution, successively with hot water, cold water and deionized water, it is rinsed well, then dry at 80 ℃~120 ℃.
In described sintered Nd-Fe-B permanent magnet, the quality percentage composition of neodymium, iron, boron is respectively 26.7%, 72.3% and 1.0%.
Described sintered Nd-Fe-B permanent magnet is replaceable is one of carbon steel, aluminium alloy, magnalium.
beneficial effect of the present invention is: (1) of the present invention in sintered Nd-Fe-B permanent magnet surface nickel phosphorus chemistry alloy plating coating evenly grafting have the solution alkalization/thermal induction Chemical Grafting Technique of the diactinic functional group of sulfonic acid of cation selective, adopt polyvinylidene difluoride (PVDF), 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid, acrylamide, methylene-bisacrylamide and ammonium persulphate are main agents, have simple to operate, the advantages such as grafting is even, and improved the performance of the anti-sodium chloride medium corrosion of conventional chemical plating nickel-phosphorus alloy coating, improved the performance of nickel-phosphorus alloy coating chloride ion corrosion, (2) adopt chemical modification technique of the present invention, realized that not only nickel-phosphorus alloy coating effectively suppresses and slow down the migration infiltration of aggressiveness chlorion, and effectively eliminated the corrosion harmfulness that in the corrosive medium, chlorion exists metallic substance, improve the barrier propterty of nickel-phosphorus alloy coating to sintered Nd-Fe-B permanent magnet, expanded the Application Areas of sintered Nd-Fe-B permanent magnet.
Embodiment
The below is described in further detail specific implementation method of the present invention.
The present embodiment adopts chemical modifying process of the present invention, nickel phosphorus alloy plating on surface of sintered neodymium iron boron permanent magnet is carried out the corrosion resisting property improvement, with solution alkalization/thermal induction Chemical Grafting Technique, the ni-p electroless plating alloy layer is carried out the technological process of chemical modification on the sintered Nd-Fe-B permanent magnet surface, concrete steps are as follows:
(1) pre-treatment on sintered Nd-Fe-B permanent magnet surface:
At first, with the sand paper of 40#, 80#, 300#, polished in the sintered Nd-Fe-B permanent magnet surface successively, and then adopt successively 600#, 800# and 1000# waterproof abrasive paper to carry out fine grinding to magnet surface, and clean up with deionized water, make its surface clean, smooth, smooth;
Magnet after polished finish is carried out sealing surface pore, at first boil 5min in deionized water, then magnet is placed in ultrasound bath and processes 1min, remove its surperficial metal fragment and other impurity;
The magnet surface sealing of hole carries out electrochemical deoiling to it after disposing, and the oil removing solution composition is: sodium phosphate 70g/L, and sodium carbonate 50g/L, sodium hydroxide 10g/L, degreasing fluid pH value adopts acetic acid to be adjusted into 9~10; Magnet is placed in degreasing fluid, and controlling the degreasing fluid temperature is 65 ℃, and the auxiliary oil removing time of ultrasonic wave is 3min; After oil removing, at first magnet adopts 55 ℃~65 ℃ hot water to carry out the auxiliary cleaning of ultrasonic wave, and then adopts flowing cool water to rinse, and guarantees the not residual any degreasing fluid of magnet surface;
Carry out surface activation process after the magnet oil removing is complete, activation solution consist of nitric acid 120g/L, urea 10g/L; Magnet is placed in activation solution, and activation temperature is 25 ℃, and soak time is 45s; After activation, at first magnet adopts 55 ℃~65 ℃ hot water to clean, and then adopts flowing cool water to rinse, and guarantees the not residual any activation solution of magnet surface;
After activation finishes, magnet is soaked zinc-nickel and process, soak the zinc-nickel solution composition and be: basic nickel carbonate 4g/L, zinc oxide 8g/L, hydrofluoric acid 80g/L soaks the zinc-nickel time to be controlled to be 60s;
Magnet soaks 60s in soaking zinc-nickel solution after, rapidly it is taken out from soaking zinc-nickel solution, the sodium hypophosphite solution that is placed in immediately concentration and is 20g/L is reduced, the zinc, the nickel fine particle that make the magnet surface deposition have catalytic activity, reduction temperature is room temperature, after magnet reduced in sodium hypophosphite solution and processes 60s, taking-up cleaned up it with deionized water.
(2) in the preparation of sintered Nd-Fe-B permanent magnet surface employing chemically plating for the nickel-phosphorus alloy coating chemical plating fluid used of surface doping polyvinylidene difluoride (PVDF) particulate:
The process for preparation of 1L plating solution is: in beaker, with 25g single nickel salt, 15g lactic acid, 6g citric acid, 5g sodium acetate, 5g succinic acid, 5g ammonium bifluoride, the 10mg Potassium Iodate dissolves with deionized water or distilled water, during dissolving, temperature is 40 ℃~50 ℃, after each reagent dissolves fully, bath temperature is cooled to room temperature;
In another beaker, the 30g sodium hypophosphite is at room temperature dissolved with appropriate deionized water or distilled water;
Above-mentioned two kinds of solution are mixed, and fully stir, then regulate the pH value of plating solution with ammoniacal liquor, the pH value that makes plating solution is 4.8;
with the anhydrous alcohol solution of 0.4g fluorine carbon type cats product with 5mL, and solution is fully mixed with 5g polyvinylidene difluoride (PVDF) particulate, fluorine carbon type cats product model is FC-4, the FC-4 cats product is commercially available, contain perfluoroalkyl long-chain and quaternary ammonium salt functional group in its molecular structure, can guarantee that the polyvinylidene difluoride (PVDF) particle fully disperses in plating solution, effectively avoid the polyvinylidene difluoride (PVDF) particulate coalescent agglomerating, for guaranteeing the FC-4 tensio-active agent to the abundant wetting of polyvinylidene difluoride (PVDF) particulate and disperseing, in the plating process, bath temperature should be between 70 ℃~95 ℃, the pH value should be between 4.0~5.4, the particle diameter of polyvinylidene difluoride (PVDF) particle is 0.5 μ m~5 μ m, then the mixed solution of fluorine carbon type cats product and polyvinylidene difluoride (PVDF) particle is slowly joined above-mentioned pH value and is in 4.8 plating solution, and magnetic agitation makes in plating solution each component fully mix,
After tensio-active agent and polyvinylidene difluoride (PVDF) particulate mixed solution add fully, bath temperature slowly is elevated to 85 ℃~90 ℃.
(3) preparation of the nickel-phosphorus alloy coating of electroless plating surface doping polyvinylidene difluoride (PVDF) particulate:
To be positioned over rapidly in chemical plating fluid through the sintered Nd-Fe-B permanent magnet that processed step (1) and carry out plating, magnetic agitation, keeping bath temperature is 85 ℃~90 ℃;
After 90min, the sintered Nd-Fe-B permanent magnet plating piece is taken out from plating solution, successively with hot water, cold water and deionized water, it is rinsed well, then carry out drying and processing at 80 ℃~120 ℃.
(4) the solution alkalinisation treatment of chemical nickeling phosphorus alloy film:
At first chemical nickeling phosphorus alloy film uses ultrasonic cleaning 3~5min; And use the deionized water clean surface, and then it is immersed in the sodium hydroxide solution that concentration is 80g/L, soaking at room temperature 15min, making has carbon-carbon double bond to generate on the polyvinylidene difluoride (PVDF) particulate in coating.
(5) preparation of 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid chemical modification liquid:
The process for preparation of 1L2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid chemical modification liquid is: with the 2-acrylamido of 100g-2-methyl isophthalic acid-propane sulfonic acid with deionized water or distilled water dissolving;
After 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid dissolves fully, successively 5g acrylamide, 6g methylene-bisacrylamide and 5g ammonium persulphate are joined in mentioned solution, stir fully dissolving, it is fully mixed;
In the process for preparation of chemical modification liquid, guarantee that solution temperature can not be over 50 ℃.
(6) preparation of 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid Modified Nickel phosphorus chemistry alloy plating coating:
To be dipped in the prepared chemical modification liquid of step (5) through the chemical nickeling phosphorus alloy film after the sodium hydroxide solution alkalinisation treatment in step (4), soak time is 25min;
After 25min, chemical nickeling phosphorus alloy film is taken out from chemical modification liquid, remove the unnecessary solution in its surface, be placed in well heater and heat-treat, keep 80 ℃~120 ℃ of temperature, heat treatment time is 20~30min, and thermal treatment is carried out in air;
After thermal treatment finishes, at first chemical nickeling phosphorus alloy film was used 95% ethanolic soln soaking at room temperature 30 minutes, then rinse well with deionized water, dry at 80 ℃~120 ℃ temperature at last.