CN101226800B - Surface treating method for sintering type Nd iron boron permanent magnetic material - Google Patents
Surface treating method for sintering type Nd iron boron permanent magnetic material Download PDFInfo
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- CN101226800B CN101226800B CN2007100930960A CN200710093096A CN101226800B CN 101226800 B CN101226800 B CN 101226800B CN 2007100930960 A CN2007100930960 A CN 2007100930960A CN 200710093096 A CN200710093096 A CN 200710093096A CN 101226800 B CN101226800 B CN 101226800B
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Abstract
A surface treating method used for sintered neodymium iron boron permanent magnets materials is characterized by nanometer composite electric plating on the surface of the material n-TiO2 / Ni, namely the TiO2 is nanoscale rutile TiO2 particles or / and nanoscale anatase TiO2 particles. Sintered NdFeb permanent magnets material treated by the invention has greatly increased corrosion resisting property. Further the invention has easily controlled technique condition and low cost, which is easy to realize industrialization.
Description
Technical field
The present invention relates to the surface treatment of metal material, specifically a kind of surface treatment method that is used for sintering type Nd iron boron permanent magnetic material.
Background technology
Since third generation permanent magnet neodymium iron boron (NdFeB) permanent magnetic material in 1984 comes out, just with its excellent magnetism can and cheap price and walk out the new lover that the laboratory becomes magnetic material in the global industrial circle rapidly.The NdFeB permanent magnet is the very high accumulator of a kind of energy, utilize it can realize the mutual conversion of energy and information expeditiously, and the energy of itself does not consume.Modern science and technology and information industry forward are integrated, the development of lightweight, intelligent direction, and have the appearance of the NdFeB permanent magnetic material of superenergy density, effectively promote the modern science and technology and the information industry development.At present, own having obtained in fields such as microwave technology, audio-visual technology, electrical engineering, instrumental technique, computer technology, magnetic separation technique, biotechnology, auto industrys of this material used widely.In Japan, the U.S., EU member country, computer hard disc driver (HDD) is its direction of mainly using, secondly is the application at aspects such as motor (MOTOR), computer, industrial automation, office automation, household electrical appliances, human body NMR imaging instrument (MRI), communication, instruments.Chinese NdFeB magnet is obtained development at full speed in nearly ten years, and the sales volume of slug type NdFeB is identical with Japan, respectively accounts for about 41% of the whole world, is called as rising sun-industry, cross-centennial industry.
There is the weakness that very easily is corroded in neodymium iron boron (NdFeB) though permanent magnetic material has above-mentioned many excellent properties.Cause that it easily is corroded former because: this material contains rare earth element nd, and Nd has very high metal active, very low (the standard electrode potential E of electrode potential
θ(Nd
3+/ Nd)=-2.431V), in atmosphere especially moist environment, can be corroded very soon; In addition, also with the heterogeneous structure of this material with and the difference of each alternate electrochemical bit relevant, make it be easy to take place electrochemical corrosion.The environment that the NdFeB magnet easily corrodes has: (1) warm wet air-flow; (2) electrochemical environment; (3) long hot environment (＞250 ℃).So this type of material all needs protective layer in use; generally be electrodeposited coating, this point whole world is substantially all the same, China and other countries (especially Japan) on the different adhesion and stability that just are coating; the coating of China is easy to come off, and Japanese can not.Obviously the research of China corrosion and protection aspect still lags behind the growth requirement of these high-tech sectors, thereby has limited further applying and the international competition strength of China of slug type NdFeB magnet greatly.
The processing method that present stage is improved its decay resistance mainly contains following two aspects:
The first is come the decay resistance of enhancing magnet self by the processing method of adding alloying element.The result of study of SUMITOMO CHEMICAL Metaux Speciaux S. A. shows that partly substituting Fe with Co is one of corrosion proof effective ways of enhancing magnet, but also can cause the decline of its magnetic property simultaneously.After crossing people such as tame coltfoal add rare earth element Dy in the NdFeB alloy, corrosion resistance improves, add Al after, then corrosion resistance descends to some extent.Though by substituting and adding element and can improve corrosion resistance to some extent, this method also has many defectives, after adding the Cr element, can damage the magnetic characteristic of magnet and quicken the dissolving of magnet when the reinforcing yin essence utmost point polarizes; The addition of Co can reduce the coercive force of magnet during greater than 10% (wt); In addition, add the price that alloying element also will improve magnet.All can influence its magnetic property by adding the corrosion proof while that some unit usually increases substantially magnet itself in a word, just say on this meaning that alloying processing method is not suitable for solving the corrosion-resistant problem of NdFeB magnet.
It two is that magnet is carried out the decay resistance that surface modification improves magnet.Magnet protection at present promptly uses coating (or coating) to stop air, moisture or the infiltration of other corrosive substance still based on the external coating overcoat, thereby improves the resistance to corrosion of magnet.The protective treatment of slug type NdFeB permanent magnetic material surface mainly is that protective layer is implemented on its surface, anti-corrosion protective layer mainly contain the coat of metal, polymer coating, conversion rete and compoundly be coated with, coating etc.On coating was handled, a lot of scholars adopted chemical plating, electroplating technology to obtain the protective layer with corrosion resisting property on slug type NdFeB surface at present.And electroplate most widely used is electrogalvanizing and electronickelling, mainly is divided in the aqueous solution and the plating in organic solution.In actual production, the not good shortcoming of ubiquity electrodeposited coating barrier propterty, on the one hand this is relevant with electroplating technology technology itself, as the composition of plating bath and stability, pre-treating technology, electroplating technology etc.; Also much relations are arranged on the other hand with the high activity Nd element of slug type NdFeB magnet material and the characteristics of powder metallurgical sintering process.In the electroplating technology process, be difficult to avoid water, acid, alkali and plating bath to infiltrate in the magnet material; In addition, in electroplating process, material has separating out of hydrogen as negative electrode, and this also is difficult to be avoided, and these combined factors get up often to cause plating that the back magnet becomes fragile, efflorescence, whiting and coating bubbling.Scholar's research chemical plating protective layer is also arranged, though chemical plating have its advantage as: dispersibility is strong, is profiling coating basically, is particularly suitable for for the part plating of complex-shaped band aperture blind hole, and coating has excellent corrosion resistance and resistance to wear etc.But, this method also have obvious defects as: cost electroplate much higher, bath stability is relatively poor, have hydrogen to separate out to the material plating time and cause that material is inhaled hydrogen and hydrogen embrittlement, coating have hole etc.Be not suitable for using under hot conditions for the NdFeB that implements behind the organic coating in addition, and organic coating has requirement to operational environment, the anti-corrosion time is not long.Its process conditions harshness of vacuum ionic electroplating method also has difficulties or the like in industrialization.Generally speaking, only implement traditional to be coated with at slug type NdFeB permanent magnetic material surface, coating handles the premium properties that increases substantially slug type NdFeB permanent magnetic material corrosion resistance and do not influence its magnet itself and remains in many problems to be solved.
Summary of the invention
Purpose of the present invention just be to provide a kind of with low cost, can increase substantially slug type NdFeB permanent magnetic material corrosion resistance and not influence the surface treatment method of the premium properties of its magnet itself, thereby make slug type NdFeB permanent magnetic material have good application prospects.
The object of the present invention is achieved like this: a kind of surface treatment method that is used for sintering type Nd iron boron permanent magnetic material is characterized in that composite plating n-TiO is carried out on the above-mentioned material surface
2/ Ni.
In order to improve above-mentioned composite plating n-TiO
2The corrosion resistance of/Ni, and the various performances of coating are improved greatly has the two-fold advantage of matrix metal and nano particle concurrently, and at aspect excellent performances such as mechanical, corrosion-resistant, electro-catalysis and photolytic activities, above-mentioned plating is nano compound electroplating n-TiO
2/ Ni, i.e. TiO wherein
2Be nano level rutile TiO
2Particle is or/and nano level Detitanium-ore-type TiO
2Particle makes its material surface energy after plating form the fine and close n-TiO with highly corrosion resistant performance
2/ Ni electrodeposited coating.
Above-mentioned nano compound electroplating n-TiO
2Among/the Ni:
The nano compound electroplating aqueous solution mainly consists of NiSO
46H
2O 250～300gL
-1, NiCl
26H
2O 30～50gL
-1, H
3BO
330～40gL
-1, an amount of surfactant, an amount of brightener and nano level rutile TiO
2Or/and nano level Detitanium-ore-type TiO
26～28gL
-1Wherein an amount of surfactant is preferably lauryl sodium sulfate 0.25～1.1gL
-1, an amount of brightener is preferably 1,4-butynediols 0.3～0.5gL
-1, asccharin 0.6～1.0gL
-1With cumarin 0.1～0.2gL
-1
The pH=3.8 of the nano compound electroplating aqueous solution～4.6, temperature are 45～55 ℃; Electroplating time 30～60 minutes; Current density is 1～2.5Adm in the electroplating process
-2Adopt batch (-type) to stir in the electroplating process.
Consider above-mentioned nano compound electroplating n-TiO
2Nano particle dispersed uniform and deposition rate among/the Ni are to help forming the fine and close n-TiO with highly corrosion resistant performance
2/ Ni electrodeposited coating, above-mentioned nanoscale TiO
2Particle preferably carries out preliminary treatment before adding the nano compound electroplating aqueous solution: promptly boil in weight percent concentration is 10～20% NaOH solution earlier, then with the clear water washing, again at dilute acid soln (for example 1: 1HNO
3Solution or 1: clear water washing again after cleaning 1HCl solution), slowly join at last in the nano compound electroplating aqueous solution, disperse about 30 minutes with ultrasonic wave, and before plating, stirred again 30～60 minutes.
In order to overcome the not good shortcoming of ubiquitous electrodeposited coating barrier propterty in the prior art, consider the high activity Nd element of slug type NdFeB magnet material and the characteristics of powder metallurgical sintering process simultaneously, avoid infiltrating in the magnet material above-mentioned nano compound electroplating n-TiO at electroplating technology process water, acid, alkali and plating bath
2To carry out phosphatization before the/Ni and handle, be about to above-mentioned material and immerse in the phosphatization aqueous solution, make material surface form the phosphating coat protective layer earlier.
In order to obtain fine and close phosphating coat protective layer uniformly, above-mentioned phosphatization liquid consist of KH
2PO
450～60gL
-1, 85% H
3PO
410～15mLL
-1With adding an amount of molybdate is promoter, and places 45～55 ℃ of water-baths, and phosphatization was handled 30～50 minutes under air blast stirs, and makes material surface form blue phosphorization membrane.
Because phosphorization membrane all contains certain crystallization water, in order to remove the crystallization water of part phosphating coat, and then improve the performance of phosphating coat, so it is dry and be incubated 30～60 minutes to be better than 135～180 ℃ of bakings most.
For the adhesion of reinforcing material surface with phosphorization membrane, above-mentioned phosphatization also will be carried out surface finish, electrochemical deoiling and acid pickling and rust removing with above-mentioned material before handling.Wherein in the surface finish according to the material shape characteristics, adopt modes such as sandblast, barreling, mechanical polishing or grinding, through coarse sand, fine sand and emery paper polishing, make surface roughness reach 6～8.In the electrochemical deoiling, the inventor thinks and should not adopt electrochemical degreasing and Solvent degreasing according to the characteristics of slug type NdFeB material surface.Electrochemical deoiling among the present invention is to be 65～70 ℃ and to consist of Na in temperature
2CO
350gL
-1, Na
3PO
412H
2O 70gL
-1, NaOH 10gL
-1, OP-10 emulsifying agent 0.5gL
-1With lauryl sodium sulfate 0.5gL
-1Mixed liquor in, regulate pH=10～11 with formic acid, with ultrasonic wave oil removing 1～5 minute.Acid pickling and rust removing is to be 65～68%HNO in concentration
320～50mLL
-1In the solution, add methylene tetramine 2gL six times
-1With lauryl sodium sulfate 0.5～1.0gL
-1, 10～30 seconds of pickling at room temperature; Wherein six methylene tetramines can reduce sour corrosivity as corrosion inhibiter, prevent that excessive erosion and the hydrogen embrittlement of slug type NdFeB material in the acid pickling and rust removing process from producing; Lauryl sodium sulfate is improved the effect of impregnation may of slug type NdFeB material surface as surfactant.Except that adding corrosion inhibiter, needs prevent the excessive erosion generation in the above-mentioned acid pickling and rust removing process, should constantly stir the pickling material simultaneously, and the strict control pickling time, the silver gray that presents careful homogeneous band gloss when the pickling material surface gets final product, and plays rust cleaning and bright dipping double action.
Because phosphorization membrane is a kind of phosphate of nonmetallic, nonconducting, porous, in order to implement nano compound electroplating n-TiO effectively on the phosphorization membrane surface
2/ Ni also need carry out preliminary treatment before implementing plating, the material surface that is about to after phosphatization is handled carries out pickling, activation and water cleaning.
Above-mentioned pickling is 10～30 seconds of pickling at room temperature, the HNO that consists of concentration 65～68% of pickle
320～50mLL
-1, six methylene tetramine 2gL
-1With lauryl sodium sulfate 0.5～1.0gL
-1, with distilled water material surface is cleaned up after the pickling; Pickling should prevent that the excessive erosion of slug type NdFeB material and hydrogen embrittlement from producing, and need make the material surface alligatoring again, impels the electro-deposition of material surface when nano compound electroplating effectively to carry out.Above-mentioned activation is an activation processing 10～30 seconds at room temperature, activating solution consist of PdCl
20.2～0.5gL
-1HCl 5～10mLL with concentration 36～38%
-1, the purpose of activation is to make material surface adsorb a certain amount of active centre, to bring out follow-up nano compound electroplating, strengthens nano compound electroplating n-TiO
2The adhesive force of/Ni layer, and after the activated processing, the each point electromotive force of material surface reaches unanimity, and helps obtaining uniform nano compound electroplating n-TiO
2/ Ni sedimentary deposit.Above-mentioned water cleans and is the distilled water cleaning.
Specifically, the surface treatment method of above-mentioned slug type NdFeB permanent magnetic material, it may further comprise the steps:
At first the surface of above-mentioned material is carried out surface finish, electrochemical deoiling and acid pickling and rust removing successively: i.e. surface finish is to make the material surface roughness reach 6～8; Electrochemical deoiling is to be 65～70 ℃ and to consist of Na in temperature
2CO
350g.L
-1, Na
3PO
412H
2O 70gL
-1, NaOH 10gL
-1, OP-10 emulsifying agent 0.5gL
-1With lauryl sodium sulfate 0.5gL
-1Mixed aqueous solution in, regulate pH=10～11 with formic acid, with ultrasonic wave oil removing 1～5 minute; Acid pickling and rust removing is 10～30 seconds of pickling at room temperature, pickle consist of concentration 65～68%HNO
320～50mLL
-1, six methylene tetramine 2gL
-1With lauryl sodium sulfate 0.5～1.0gL
-1
Carrying out phosphatization then handles: be about to described material and immerse in the phosphatization liquid, and place 45～55 ℃ of water-baths, phosphatization was handled 30～50 minutes under air blast stirs, and made material surface form blue phosphorization membrane, and toasted drying and be incubated 30～60 minutes in 135～180 ℃; Wherein phosphatization liquid consists of KH
2PO
455gL
-1, concentration 85% H
3PO
410mLL
-1With an amount of molybdate;
Above-mentioned material after again phosphatization being handled carries out pickling, activation and distilled water successively and cleans; Wherein pickling is 10 seconds of pickling at room temperature, the HNO that consists of concentration 65～68% of pickle
320～50mLL
-1, six methylene tetramine 2gL
-1With lauryl sodium sulfate 0.5～1.0gL
-1, with distilled water material surface is cleaned up after the pickling; Activation is 20 seconds of activation processing at room temperature, activating solution consist of PdCl
20.2～0.5gL
-1HCl 5～10mLL with concentration 36～38%
-1The activation back is cleaned with distilled water; Last material surface after above-mentioned processing carries out nano compound electroplating n-TiO
2/ Ni: wherein the nano compound electroplating aqueous solution consists of NiSO
46H
2O 270gL
-1, NiCl
26H
2O45gL
-1, H
3BO
338gL
-1, lauryl sodium sulfate 0.4gL
-1, 1,4-butynediols 0.4gL
-1, asccharin 0.82gL
-1, cumarin 0.2gL
-1Rutile TiO with 50nm
2Particle is or/and the Detitanium-ore-type TiO of 10nm
2Particle 24gL
-1
Above-mentioned nanoscale TiO
2Particle preferably carries out preliminary treatment before adding the nano compound electroplating aqueous solution: promptly boil in weight percent concentration is 10～20% NaOH solution earlier, then with the clear water washing, again at dilute acid soln (for example 1: 1HNO
3Or 1: clear water washing again after cleaning 1HCl solution), last slowly the adding in the nano compound electroplating aqueous solution, disperseed 30 minutes with ultrasonic wave, and stirred before the plating 30 minutes again.
The pH=4.2 of above-mentioned electroplate liquid, temperature is 50 ℃, the current density in the plating is 2Adm
-2, electroplated 60 minutes, adopt batch (-type) to stir in the electroplating process;
In order to improve nano compound electroplating n-TiO
2The performance of/Ni layer is eliminated the coating internal stress, after plating is finished, cleans with 45～55 ℃ distilled water, and back cold water cleans, and in 135～180 ℃ of heat treatments 30～60 minutes.
In the present invention; in order to overcome the not good shortcoming of ubiquitous electrodeposited coating barrier propterty in the prior art; consider the high activity Nd element of slug type NdFeB magnet material and the characteristics of powder metallurgical sintering process simultaneously; avoid at the electroplating technology process water; acid; alkali and plating bath infiltrate in the slug type NdFeB magnet material; the magnet that easily causes after avoiding electroplating becomes fragile; efflorescence; defectives such as whiting and coating bubbling; the inventor has proposed the surface treatment method at slug type NdFeB permanent magnetic material surface design gradient protective layer; promptly form phosphorization membrane earlier, carry out nano compound electroplating n-TiO again at slug type NdFeB permanent magnetic material surface
2/ Ni layer has very strong advantage for the decay resistance that increases substantially slug type NdFeB permanent magnetic material under the condition that does not influence the premium properties of its magnet own.
In order to obtain the adhesion of densification, even, nontoxic, pollution-free, the transitional phosphating coat protective layer of protecting and enhancing slug type NdFeB permanent magnetic material surface and phosphating coat protective layer at slug type NdFeB permanent magnetic material surface, the inventor has proposed concrete phosphorization treatment process parameter and the preceding technological parameters such as surface finish, electrochemical deoiling and acid pickling and rust removing of phosphatization processing in the present invention according to the characteristics of slug type NdFeB material surface.By phosphorization treatment process,, transform film by chemical reaction generation one deck phosphate chemical nonmetallic, nonconducting, porous at slug type NdFeB material surface.Also because its phosphating coat has porousness, the coating in follow-up electroplating processes technology can penetrate in these holes, thereby can significantly improve the adhesion of phosphorization membrane and coating.Phosphating coat can make slug type NdFeB material surface change non-conductor into by excellence conductor again in addition, thereby has suppressed the formation of surperficial micro cell, has hindered the corrosion of slug type NdFeB material surface effectively, can improve its corrosion resistance and resistance to water exponentially.
Also adopted new electroplating technology-nano compound electroplating n-TiO among the present invention simultaneously
2/ Ni.At nano compound electroplating n-TiO
2Among/the Ni, because TiO
2The existence of nano particle will influence the electrocrystallization process of matrix metal, make the greatly refinement of crystal grain of matrix metal, sometimes in addition the grain refinement that can make matrix metal to nanoscale, become nanocrystalline, the various performances of coating are improved greatly, have the two-fold advantage of matrix metal and nano particle concurrently, at aspect excellent performances such as mechanical, corrosion-resistant, electro-catalysis and photolytic activities, thereby not only improved the decay resistance of slug type NdFeB permanent magnetic material effectively significantly, and made slug type NdFeB permanent magnetic material have good application prospects.
In order to implement nano compound electroplating n-TiO effectively on the phosphorization membrane surface
2/ Ni helps obtaining uniform nano compound electroplating n-TiO
2/ Ni sedimentary deposit, defectives such as the magnet that easily causes after avoiding electroplating becomes fragile, efflorescence, whiting and coating bubbling, the present invention has not only proposed implementing nano compound electroplating n-TiO
2The preliminary treatment that/Ni carries out before electroplating is pickling, activation and water cleaning process parameter, but also concrete nano compound electroplating n-TiO is provided
2The relevant parameter of/Ni is as the composition of plating bath, electroplating technological parameter etc.
In a word, slug type NdFeB permanent magnetic material by the present invention's processing, its corrosion resisting property increases substantially (referring to the experimental data among the embodiment 1), and the premium properties of its magnet material itself is unaffected, thereby makes slug type NdFeB permanent magnetic material have good application prospects.Process conditions of the present invention are easy to control, and are with low cost, easy realization of industrialization.
Description of drawings
Fig. 1 is that sample in the embodiment of the invention 1 is at the 3.5%NaCl of not deoxygenation electrolyte solution polarization curve, wherein number 1 and be the sample of slug type NdFeB matrix after handling by the present invention, numbering 2 is a slug type NdFeB matrix electroplated Ni layer sample, numbering 3 is the sample after slug type NdFeB matrix phosphatization is handled, and numbering 4 is a slug type NdFeB matrix;
Fig. 2 is that sample in the embodiment of the invention 1 is respectively at 5%H
2SO
4And 6%FeCl
3Corrode immersion test figure as a result in the corrosive liquid;
Fig. 3 is the hole test experiments figure as a result of the sample in the embodiment of the invention 1;
Fig. 4 is the thermal shock circulation experiment figure as a result of the sample in the embodiment of the invention 1;
Among Fig. 2～Fig. 4, numbering a is the sample after slug type NdFeB matrix is handled by the present invention, and numbering b is that slug type NdFeB matrix phosphatization is handled back electroplated Ni layer sample; Numbering c is a slug type NdFeB matrix electroplated Ni layer sample.
Embodiment
Further specify the present invention by the following examples, but the present invention is not limited to these embodiment.
Embodiment 1: a kind of surface treatment method of sintering type Nd iron boron permanent magnetic material, and its step is as follows:
At first carry out surface finish, electrochemical deoiling and acid pickling and rust removing successively at slug type NdFeB material surface.Wherein surface finish is through coarse sand, fine sand, emery paper polishing, makes surface roughness be about 7, electrochemical deoiling again after cleaning with clear water; Electrochemical deoiling is to be 67 ℃ and to consist of 50gL in temperature
-1Na
2CO
3, 70gL
-1Na
3PO
412H
2O, 10gL
-1NaOH, 0.5gL
-1OP-10 emulsifying agent and 0.5gL
-1The mixed aqueous solution of lauryl sodium sulfate, it is 10.78 that formic acid is regulated pH, ultrasonic wave oil removing 3 minutes; About 65 ℃ distilled water cleans, and cold water cleans again, after 20 seconds of acid pickling and rust removing at room temperature, pickle consist of 35mLL
-1The HNO of concentration 65～68%
3, 2gL
-1Six methylene tetramines and 0.7gL
-1Lauryl sodium sulfate, repeatedly distilled water cleaning fast after pickling is finished.
Carrying out phosphatization then handles: be about to material and adopt the hang immersion to consist of 55gL
-1KH
2PO
4, 12mLL
-1The H of concentration 85%
3PO
4With with 0.4gL
-1Molybdate is in the phosphatization liquid of promoter, and places 50 ℃ of water-baths, and phosphatization was handled 40 minutes under air blast stirs, and makes material surface form blue phosphorization membrane, and it is dry in 150 ℃ of bakings to clean the back, and is incubated 45 minutes.
Material after again phosphatization being handled carries out pickling, activation and distilled water successively and cleans.Wherein pickling is to consist of 35mLL
-1The HNO of concentration 65～68%
3, 2gL
-1Six methylene tetramines and 0.7gL
-1In the pickle of lauryl sodium sulfate, 20 seconds of pickling at room temperature; Activation is to consist of 0.3gL
-1PdCl
2And 7mLL
-1In the mixed liquor of the HCl of concentration 36～38%, activation processing is 20 seconds under the room temperature, and the back is cleaned with distilled water.
Last material surface after above-mentioned processing carries out nano compound electroplating n-TiO
2/ Ni; Wherein the nano compound electroplating aqueous solution consists of 270gL
-1NiSO
46H
2O, 40gL
-1NiCl
26H
2O, 35gL
-1H
3BO
3, 0.75gL
-1Lauryl sodium sulfate, 0.4gL
-11,4-butynediols, 0.8gL
-1Asccharin, 0.15gL
-1The Detitanium-ore-type TiO of cumarin and 10nm
2Particle 24gL
-1The pH=4.13 of electroplate liquid, temperature is 50 ℃, the current density in the plating is 2Adm
-2, electroplated 50 minutes, adopt batch (-type) to stir in the electroplating process;
The Detitanium-ore-type TiO of above-mentioned 10nm
2Particle will carry out preliminary treatment before adding the nano compound electroplating aqueous solution: promptly boil in weight percent concentration is 15% NaOH solution earlier, then with the clear water washing, again 1: 1HNO
3Clear water washing again after cleaning in the solution, after slowly join in the nano compound electroplating aqueous solution, disperse about 30 minutes with ultrasonic wave, and stirred again before the plating 30 minutes;
After plating is finished, clean with 50 ℃ distilled water, back cold water cleans, in 160 ℃ of heat treatments 50 minutes, to eliminate the coating internal stress.
Carry out following Performance Detection with above-mentioned by the sample after the present invention's processing:
A, corrosion resistance: referring to accompanying drawing 1 be sample at the 3.5%NaCl of not deoxygenation electrolyte solution polarization curve, its characteristic parameter is listed in table 1.As seen improve 670mV by the spontaneous potential of the sample after the present invention's processing than blank sample (slug type NdFeB matrix) by Fig. 1 and table 1; corrosion electric current density reduces an order of magnitude; the polarization impedance value also improves nearly 20 times, shows by the sintering type Nd iron boron permanent magnetic material after the present invention's processing to have good protective effect in chloride environment.
Table 1 sample is in 3.5%NaCl electrolyte solution polarization curve test data
| Specimen coding | Spontaneous potential E/mV | Corrosion electric current density I/uAcm -2 | Polarization impedance R/Kohmcm 2 | Remarks |
| 1 | -138.3 | 1.11 | 19.58 | Sample after slug type NdFeB matrix is handled by the present invention |
| 2 | -541.1 | 7.111 | 3.06 | Slug type NdFeB matrix electroplated Ni layer sample |
| 3 | -751.2 | 15.826 | 1.37 | Slug type NdFeB matrix phosphatization is handled sample |
| 4 | -809.7 | 23.38 | 0.93 | Slug type NdFeB matrix |
B, by the corrosion immersion test: sample is at 5%H
2SO
4Corrosive liquid and 6%FeCl
3The corrosion soak test the results are shown in Figure 2.Sample after handling by the present invention as seen from Figure 2 is at 5%H
2SO
4The anti-corrosion time obviously is longer than the electroplated Ni layer sample, especially at 6%FeCl
3In the corrosive liquid environment, show that the corrosion resisting property after sintering type Nd iron boron permanent magnetic material is handled by the present invention is best.
C, hole test experiments: paste filter paper method by standard and detect (GB5935-86), the results are shown in Figure 3.Nano compound electroplating n-TiO after handling by the present invention as seen from Figure 3
2/ Ni layer porosity is zero, and showing by the sample after the present invention's processing does not have hole, nano compound electroplating n-TiO
2The densification of/Ni layer.
D, thermal shock circulation experiment: detect adhesion, experimental condition is that sample is warming up to and takes out that to immerse cold water immediately be a circulation behind 400 ℃ of constant temperature 30min, and whether have peeling, obscission, the results are shown in Figure 4 if observing specimen surface.Sample after handling by the present invention does not as seen from Figure 4 see that through 12 thermal shock cyclic tests peeling comes off yet, and the sample of electroplated Ni just sees that through 2 thermal shock cyclic tests peeling comes off, and shows the nano compound electroplating n-TiO among the present invention
2/ Ni layer strong adhesion.
Embodiment 2: a kind of surface treatment method of sintering type Nd iron boron permanent magnetic material, wherein:
15 seconds of acid pickling and rust removing before phosphatization is handled, acid washing water solution consist of 40mLL
-1The HNO of concentration 65～68%
3, 2gL
-1Six methylene tetramines and 0.8gL
-1Lauryl sodium sulfate;
Phosphatization was handled 35 minutes, made material surface form blue phosphorization membrane, and it is dry in 160 ℃ of bakings to clean the back, and is incubated 50 minutes, and phosphatization liquid consists of 57gL
-1KH
2PO
4, 13mLL
-1The H of concentration 85%
3PO
4And 0.4gL
-1Molybdate;
In the pickling and activation after phosphatization is handled: pickling is to consist of 40mLL
-1The HNO of concentration 65～68%
3, 2gL
-1Six methylene tetramines and 0.6gL
-1In the pickle of lauryl sodium sulfate, 15 seconds of pickling at room temperature; Activation is to consist of 0.4gL
-1PdCl
2And 8mLL
-1In the mixed liquor of the HCl of concentration 36～38%, activation processing is 25 seconds under the room temperature;
Nano compound electroplating n-TiO
2/ Ni: wherein electroplate liquid consists of 280gL
-1NiSO
46H
2O, 45gL
-1NiCl
26H
2O, 32gL
-1H
3BO
3, 0.9gL
-1Lauryl sodium sulfate, 0.45gL
-11,4-butynediols, 0.75gL
-1Asccharin, 0.12gL
-1The rutile TiO of cumarin and 50nm
2The Detitanium-ore-type TiO of particle and 10nm
2The mixture 20gL of particle
-1, the pH=4.3 of electroplate liquid, temperature is 52 ℃, the current density in the plating is 1.8Adm
-2, electroplating time 45 minutes adopts batch (-type) to stir in the electroplating process;
After plating is finished, in 160 ℃ of heat treatments 45 minutes.
All the other are with embodiment 1.
Embodiment 3: a kind of surface treatment method of sintering type Nd iron boron permanent magnetic material, wherein: nano compound electroplating n-TiO
2TiO among the/Ni
2Particle is the rutile TiO of 50nm
2Particle 15gL
-1All the other are with embodiment 1.
Claims (6)
1. a surface treatment method that is used for sintering type Nd iron boron permanent magnetic material is characterized in that described material surface is carried out composite plating n-TiO
2/ Ni; Nano compound electroplating n-TiO
2To carry out phosphatization before the/Ni and handle, be about to described material and immerse in the phosphatization liquid, make material surface form phosphorization membrane;
Phosphatization liquid consist of KH
2PO
450～60gL
-1, 85% H
3PO
410～15mLL
-1With an amount of molybdate;
Nano compound electroplating n-TiO
2Among/the Ni: the nano compound electroplating aqueous solution mainly consists of NiSO
46H
2O 250～300gL
-1, NiCl
26H
2O 30～50gL
-1, H
3BO
330～40gL
-1, an amount of surfactant is lauryl sodium sulfate 0.25～1.1gL
-1, an amount of brightener is 1,4-butynediols 0.3～0.5gL
-1, asccharin 0.6～1.0gL
-1With cumarin 0.1～0.2gL
-1, nano level rutile TiO
2Particle is or/and nano level Detitanium-ore-type TiO
2Particle 6～28gL
-1
The pH=3.8 of the described nano compound electroplating aqueous solution～4.6, temperature are 45～55 ℃, electroplating time 30～60 minutes; Current density is 1～2.5Adm
-2Adopt batch (-type) to stir in the electroplating process.
2. the surface treatment method of sintering type Nd iron boron permanent magnetic material according to claim 1 is characterized in that: described nanoscale TiO
2Particle will carry out preliminary treatment before adding the nano compound electroplating aqueous solution: promptly boil in weight percent concentration is 10～20% NaOH solution earlier, wash with clear water then, clear water washing again after cleaning with dilute acid soln again, slowly join in the nano compound electroplating aqueous solution at last, disperseed 30 minutes with ultrasonic wave, and stirred again before the plating 30～60 minutes.
3. the surface treatment method of sintering type Nd iron boron permanent magnetic material as claimed in claim 1 is characterized in that: before phosphatization was handled, material surface will carry out surface finish, electrochemical deoiling and acid pickling and rust removing.
4. the surface treatment method of sintering type Nd iron boron permanent magnetic material as claimed in claim 1 is characterized in that: carry out nano compound electroplating n-TiO after phosphatization is handled
2Preliminary treatment before the/Ni, promptly the material surface after phosphatization is handled carries out pickling, activation and water cleaning.
5. the surface treatment method of sintering type Nd iron boron permanent magnetic material as claimed in claim 4, it is characterized in that: described pickling is 10～30 seconds of pickling at room temperature, the HNO that consists of concentration 65～68% of pickle
320～50mLL
-1, six methylene tetramine 2gL
-1With lauryl sodium sulfate 0.5～1.0gL
-1Described activation is an activation processing 10～30 seconds at room temperature, activating solution consist of PdCl
20.2～0.5gL
-1HCl 5～10mLL with concentration 36～38%
-1
6. a surface treatment method that is used for sintering type Nd iron boron permanent magnetic material is characterized in that: described material surface is carried out composite plating n-TiO
2/ Ni;
It may further comprise the steps:
At first the surface of described material is carried out surface finish, electrochemical deoiling and acid pickling and rust removing successively: i.e. surface finish is to make the material surface roughness reach 6～8; Electrochemical deoiling is to be 65～70 ℃ and to consist of Na in temperature
2CO
350gL
-1, Na
3PO
412H
2O 70gL
-1, NaOH 10gL
-1, OP-10 emulsifying agent 0.5gL
-1With lauryl sodium sulfate 0.5gL
-1Mixed liquor in, regulate pH=10～11 with formic acid, with ultrasonic wave oil removing 1～5 minute; Acid pickling and rust removing is 10～30 seconds of pickling at room temperature, pickle consist of concentration 65～68%HNO
320～50mLL
-1, six methylene tetramine 2gL
-1With lauryl sodium sulfate 0.5～1.0gL
-1
Carrying out phosphatization then handles: be about to described material and immerse in the phosphatization liquid, and place 45～55 ℃ of water-baths, phosphatization was handled 30～50 minutes under air blast stirs, and made material surface form blue phosphorization membrane, and toasted drying and be incubated 30～60 minutes in 135～180 ℃; Wherein phosphatization liquid consists of KH
2PO
455gL
-1, concentration 85% H
3PO
410mLL
-1With an amount of molybdate;
Material after again phosphatization being handled carries out pickling, activation and distilled water successively and cleans; Wherein pickling is 10 seconds of pickling at room temperature, the HNO that consists of concentration 65～68% of pickle
320～50mLL
-1, six methylene tetramine 2gL
-1With lauryl sodium sulfate 0.5～1.0gL
-1Activation is 20 seconds of activation processing at room temperature, activating solution consist of PdCl
20.2～0.5gL
-1HCl 5～10mLL with concentration 36～38%
-1The activation back is cleaned with distilled water;
Last material surface after above-mentioned processing carries out nano compound electroplating n-TiO
2/ Ni: wherein the nano compound electroplating aqueous solution consists of NiSO
46H
2O 270gL
-1, NiCl
26H
2O 45gL
-1, H
3BO
338gL
-1, lauryl sodium sulfate 0.4gL
-1, 1,4-butynediols 0.4gL
-1, asccharin 0.82gL
-1, cumarin 0.2gL
-1Rutile TiO with 50nm
2Particle is or/and the Detitanium-ore-type TiO of 10nm
2Particle 24gL
-1Nanoscale TiO
2Particle will carry out preliminary treatment before adding the nano compound electroplating aqueous solution: promptly boil in weight percent concentration is 10～20% NaOH solution earlier, wash with clear water then, clear water washing again after in dilute acid soln, cleaning again, in the last slowly adding nano compound electroplating aqueous solution, disperseed 30 minutes with ultrasonic wave, and stirred again before the plating 30～60 minutes;
The pH=4.2 of electroplate liquid, temperature is 50 ℃, the current density in the plating is 2Adm
-2, electroplated 60 minutes, adopt batch (-type) to stir in the electroplating process;
After plating is finished in 135～180 ℃ of heat treatments 30～60 minutes.
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101728042B (en) * | 2008-10-16 | 2012-07-18 | 北京中科三环高技术股份有限公司 | Technique for treating surface of permanent magnet material |
| CN102965655B (en) * | 2012-11-23 | 2017-10-31 | 沈阳工业大学 | One kind improves the corrosion proof method of surface of Nd-Fe-B permanent magnet phosphating coat |
| CN105506582A (en) * | 2015-12-29 | 2016-04-20 | 湖南理工学院 | Method for improving corrosion resistance of neodymium iron boron magnet by using atomic layer deposition |
| CN109594070B (en) * | 2017-09-30 | 2021-02-23 | 比亚迪股份有限公司 | Neodymium iron boron phosphating solution, preparation method thereof and neodymium iron boron phosphating method |
| CN107723693A (en) * | 2017-11-03 | 2018-02-23 | 安徽新合富力科技有限公司 | A kind of Nd Fe B alloys method for bonderizing |
| CN108083793A (en) * | 2017-12-20 | 2018-05-29 | 宁波市鄞州智伴信息科技有限公司 | The formula and compounding method of a kind of ferrite permanent-magnet materials |
| CN110983395A (en) * | 2019-12-17 | 2020-04-10 | 广东小天才科技有限公司 | Magnet, preparation method and wearable device |
| CN111073466B (en) * | 2019-12-20 | 2021-04-30 | 浙江中杭新材料科技有限公司 | Preparation method of low-cost high-corrosion-resistance neodymium iron boron |
| CN112899684B (en) * | 2020-08-21 | 2023-02-03 | 天津京磁电子元件制造有限公司 | Process for electroplating copper and nickel on neodymium-iron-boron magnet |
| CN112813474B (en) * | 2020-12-28 | 2022-03-08 | 宁波韵升股份有限公司 | Process for improving surface shearing force of neodymium iron boron magnet |
| CN115367846A (en) * | 2022-08-16 | 2022-11-22 | 山东科技大学 | Super-strong magnetic inorganic flocculant, preparation method and application thereof |
| CN115985612A (en) * | 2022-12-20 | 2023-04-18 | 东莞金坤新材料股份有限公司 | Formula and preparation method of water-erosion-resistant powerful magnet |
| CN116230347A (en) * | 2023-03-01 | 2023-06-06 | 东莞金坤新材料股份有限公司 | Formula of flexible neodymium-iron-boron magnetic material and manufacturing method thereof |
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