CN100464007C - Process for preparing neodymium-iron-boron permanent magnetic material surface gradient function coating layer - Google Patents
Process for preparing neodymium-iron-boron permanent magnetic material surface gradient function coating layer Download PDFInfo
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- CN100464007C CN100464007C CNB2006100544400A CN200610054440A CN100464007C CN 100464007 C CN100464007 C CN 100464007C CN B2006100544400 A CNB2006100544400 A CN B2006100544400A CN 200610054440 A CN200610054440 A CN 200610054440A CN 100464007 C CN100464007 C CN 100464007C
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Abstract
A neodymium-iron-boron permanent magnetic materials surface gradient function coating preparation method overcomes current slug type neodymium iron boron surface processing method existent problem. Said method adopts new surface modification process means combined with tradition electroplating ( or chemical plating ) advantages and sol-gel technologic property, thereby avoiding single cladding material poor cladding material adhesion, less compactness, easy resulting slough, having pore and too thin single sol coating shortages. Said method forms tight sol coating on neodymium iron boron base material surface, to obtain oxide ceramics coating after sintering treatment, then cladding material on gel coating to form function gradient coating to take complete corrosion protection.
Description
Technical field
The present invention relates to chemical industry, metallic substance, surface modification field, belong to the surface modifying treatment of neodymium-iron-boron magnetic material, is a kind of process for preparing neodymium-iron-boron permanent magnetic material surface gradient function coating layer specifically.
Background technology
Since third generation permanent magnet NdFeB permanent magnet material in 1984 comes out, just with its excellent magnetism can and cheap price and walk out the new lover that the laboratory becomes magneticsubstance 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 magnet material of superenergy density, effectively promote the modern science and technology and the information industry development.At present, this material has obtained in fields such as microwave technology, audio-visual technology, electrical engineering, instrumental technique, computer technology, magnetic separation technique, biotechnology, automotive industrys using widely.In Japan, the U.S., EU member country, computer hard disc driver (HDD) is its direction of mainly using, next is motor (MOTOR, be applied to computer, industrial automation, office automation and household electrical appliances) and human body NMR imaging instrument (MRI), be to be applied to communication, instrument, magnetic separator nuclear power acoustic device once more.Chinese neodymium iron boron magnetic body is obtained development at full speed in nearly ten years, and the sales volume of sintered NdFeB is identical with Japan, respectively accounts for about 41% of the whole world, is called as rising sun industry, cross-centennial industry.
But because this type of permanent magnet material contains rare earth element nd on the one hand, Nd has very high metal active, very low (the normal potential E of electropotential
θ(Nd
3+/ Nd)=-2.431V), in atmosphere especially moist environment, can be corroded very soon; On the other hand, the difference with heterogeneous structure and each alternate electrochemical bit of magnet causes being easy to take place galvanic corrosion.The corrosive environment easily takes place the NdFeB magnet has: (1) warm wet air-flow; (2) electrochemical environment; (3) long hot environment (〉 is 250 ℃).So this type of material all needs protective layer in use, generally be electrolytic coating.The basic whole world of this point is all the same, China and other countries (especially Japan) on the different bonding force and stability that just are coating, the coating of China is easy to come off, and can not of Japan.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 Sintered NdFeB magnet greatly.
Present stage mainly contains two aspects to its protected mode of carrying out:
The first is come the anti-corrosion function of enhancing magnet itself by the mode 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 examines the decline of coercive force (Hci) in also can causing simultaneously.After crossing people such as tame coltfoal add Dy in the NdFeB alloy, solidity to corrosion improves, add Al after, then solidity to corrosion descends to some extent.By substituting and adding element and can improve solidity to corrosion to some extent, but this method exists many weak points, as after adding the Cr element, can damage the magnetic properties 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% (at).In addition, add the price that alloying element also will improve magnet.Also do not find at present under the situation that does not reduce magnetic properties by adding some unit and usually increase substantially the corrosion proof method of magnet itself, alloying can not fundamentally solve the etching problem of NdFeB magnet.
It two is that magnet is being carried out the performance that surface modification improves magnet.Magnet protection at present promptly uses coating (or coating) to stop air, moisture or other corrosives to permeate the resistance to corrosion that improves magnet still based on the external coating protective layer.Corrosion protection coating mainly contains: metal or alloy coating, organic or inorganic coating and compound coating.Metal or alloy coating can adopt metal and compounds such as Ni, Zn, Al, Cu, Cr, TiN, Ni-P, Ni-Cu-P, is plated to magnet surface with methods such as chemical conversion film, plating, electroless plating or vacuum coating technologies.
The chemical conversion membrane processing method is commonly used two classes: a class is that phosphoric acid salt is made membrane-forming agent, and another kind of is that chromic salt is made membrane-forming agent.At present the more sophisticated chemical conversion membrane processing method of technology is a chromate treating, is that the aqueous solution of main component carries out chemical treatment acquisition protective membrane with chromic anhydride acid and dichromate.Have preservative effect preferably though contain the chromium conversion film, and can in the environment of comparatively high temps, use after coating combines, contain hexavalent chromium ion in the chromate treating technology, have toxicity, contaminate environment, and the processing cost height of waste liquid.
Electroplating at present most widely used is electro-galvanizing and electronickelling, mainly is divided in the aqueous solution and the plating in organic solution.In actual production, the not good shortcoming of ubiquity electrolytic coating barrier propterty, on the one hand these relevant composition and stability, pre-treating technology, electroplating technology etc. as plating bath with electroplating technology technology itself.Also much relations are arranged on the other hand with the characteristics of sintered Nd Fe B magnet material.Nd in the NdFeB magnet is the extremely strong element of a kind of activity, it very easily with environment in some element (as H, O etc.) carry out chemical reaction and cause magnet corrosion; Secondly, sintered Nd Fe B adopts the repressed moulding of powder metallurgy method to make with final sintering, therefore, magnet surface is coarse, and is loose porous, and surface porosity factor is than higher, surface quality is not high, is difficult to avoid water, acid, alkali and plating bath to infiltrate in the electroplating technology process; In addition, in electroplating process, workpiece 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.
Electroless plating: people such as Li Qingyu, Yang Jianhong carry out the bright Ni-P of light-plated to the NdFeB magnet surface in homemade very small chemical coating bath, have obtained certain anti-corrosion effect.Studied chemical plating Ni-Gu-P technology on the NdFeB magnet in people such as enter a higher school, this studies show that the plating pre-treatment is the important prerequisite of carrying out electroless plating.People such as Xie Yuanshou have worked out with chemical plating method plating copper-nickelalloy or nickel-phosphorus alloy bottom on NdFeB powder metallurgy porous matrix, re-plating high-sulfur nickel and semi-bright nickel.Though electroless plating have its advantage as: dispersive ability is strong, is profiling coating basically, is particularly suitable for the part plating of complex-shaped band aperture blind hole, and coating has excellent solidity to corrosion and wear resistance etc.But, it also have tangible limitation as: cost is electroplated much higher; Bath stability is relatively poor; To the workpiece plating time, hydrogen evolution is arranged and cause workpiece suction hydrogen and hydrogen embrittlement; Coating has hole etc.When making it applying aspect the surfacecti proteon of NdFeB magnet, these can have some difficulties.
Vacuum ion plating: be to utilize vacuum evaporation or filtered cathode vacuum arc at NdFeB surface deposition Al or TiN film.People such as Zheng Guozhen have studied in NdFeB permanent magnetic material electroplating Ni, technologies such as ion plating Ti, TiN, and test-results shows that NdFeB resistance to corrosion, surface abrasion resistance, aesthetic property all improve greatly through after the above-mentioned processing.Recently according to external, adopt LPPs technology (Low Pressure Pack sublimation) to apply the Zn protective layer on the NdFeB magnet, the anti-corrosion effects of the Zn film of coating is better than electroplated Ni and electroplates Zn, and the Al protective layer that adopts the IVO method to apply.
The organic coating that is used for the NdFeB permanent magnet mainly is resin and organic polymer, secondly also has polyacrylate, poly-phthalein amine, poly-phthalimide etc.High order is far away wait the people studied the Resins, epoxy electrophoresis to NdFeB magnet coating processes with and antiseptic property, the result shows, electrophoretic coating epoxy resin layer on the NdFeB that electroplates Zn, Ni, its solidity to corrosion is much better than traditional plating Ni, plating Zn layer.At present, popular is molecular vapor deposition coating skill that is VDP (Vaporized Deposit Process) technology in the world, adopts a kind of novel high molecular polymer that is Parylene as coating material, and this coating has quite high solidity to corrosion.But this technology also has difficulties in industrialization.
Sol-Gel (sol-gel) coating technology is compared with CVD, PVD, sputter, spraying thermolysis and plasma spray coating technology, owing to have the following advantages: (1) directly obtains oxide compound, glass, pottery, inorganic-coatings such as organic double compound from liquid phase, low temperature; (2) can obtain the high and uniform matrix material of molecular level of purity; (3) do not need expensive plant and instrument; (4) simple, the good reproducibility of technology; (5) big area coating and low cost etc. be can implement, thereby people's very big interest and great attention caused.In the world the eighties just the someone begin to explore the surface property that the Sol-Gel technology is improved metal or alloy, or give the new functional performance of material surface etc., and than system with to carry out this technical study be in the early 1990s comprehensively, carried out SiO so far
2, SiO
2-TiO
2, SiO
2-Al
2O
3, SiO
2-B
2O
3, TiO
2, Al
2O
3, ZrO
2, ZrO
2-Y
2O
3, ZrO
2-CeO
2And CeO
2Deng coated material and correlation technique, and they are as the The Characteristic Study such as anti-oxidant, corrosion-resistant and wear-resisting of metal or alloy material surface coating.As the CN200510085466.7 patent application, be to adopt the technology that this routine of sol-gel processing is used to prepare powder, film coating material to be incorporated into the surperficial anodic oxidation treatment of perishable magnesium alloy.
The work of applying for a patent the aspect aspect anticorrosion at neodymium iron boron at present both at home and abroad mainly contains: Xu Zhihuai has openly invented a kind of Nd-Fe-B permanent magnet surface polyphenylene ethyl (Parylene) anti-corrosion coating and has prepared pre-washing technology, carries out the preparation of Parylen anti-corrosion coating by vapour deposition (CVD) technology; People such as Zhao Chunying combine the ability cathode electrophoresis technology with the electronickelling technology, and implement to soak nickel, plating semi-bright nickel and bright nickel plating operation in nickel plating technology; People such as Xie Ruibing adopt organic Electroplating Aluminum, obtain the fine and close aluminium metal coating of light; People such as Wu Jie are ultrasonic dispersing electroplated Ni-P on neodymium iron boron magnetic body; People such as Raducanu adopt metallic coating to strengthen the corrosion-proof wear performance of neodymium iron boron.
In sum, there is following problem in the various treatment processs in existing sintering type Nd iron boron surface:
Alloying can not fundamentally solve the etching problem of NdFeB magnet; Though some achievement on the surface modifying treatment, but still existing problems: chemical conversion film is handled the membranous crisp porous of conversion that obtains, generally can only be as decorating and middle protection operation, be not suitable for as long-term preservative protective film, and contain hexavalent chromium ion in the more sophisticated chromate treating technology, have toxicity, contaminate environment, use is under an embargo in industrialization; Electroplate in the actual production, the not good shortcoming of ubiquity electrolytic coating barrier propterty if any separating out of hydrogen, causes plating that the back magnet becomes fragile, efflorescence, whiting and coating bubbling etc.; Also have in the electroless plating tangible limitation as: cost is electroplated much higher; Bath stability is relatively poor; To the workpiece plating time, hydrogen evolution is arranged and cause workpiece suction hydrogen and hydrogen embrittlement; Coating has hole etc.; NdFeB behind the organic coating is not suitable for using under hot conditions, and organic coating has requirement to Working environment, and the anti-corrosion time is not long; The processing condition harshness of vacuum ion plating also has difficulties in industrialization etc.
Up to the present, do not see the relevant sol-gel technique of using at neodymium iron boron surface preparation sull, and on the sol pellicle layer, implement coating again, form the research report of functionally gradient protective layer.
Summary of the invention
The object of the present invention is to provide a kind of process for preparing neodymium-iron-boron permanent magnetic material surface gradient function coating layer, this method adopts colloidal sol-gel combination of oxides coating to combine with plating Ni-P coating, forms the functionally gradient protective layer, improves the Application Areas of neodymium iron boron.
The present invention realizes successively through the following steps:
(1) pre-treatment of sintered type NdFeB permanent magnet body material:
Carry out successively in ethanol, preserving after surface finish, degreasing, washing, pickling, the ultrasonic wave washing, stand-by;
Surface finish: be according to processed features of shape, adopt sandblast, barreling, mechanical polishing or grinding etc., surfaceness is reached about 7;
Degreasing: removing oil formula has many kinds, considers the loose porous situation of sintering type Nd iron boron matrix itself, selects following Recipe: NaOH:60g/L; Na
3PO
412H
2O:15g/L; Room temperature; 10min; Add an amount of tensio-active agent sodium lauryl sulphate, ultrasonic agitation is cleaned;
Pickling: after carrying out previous processed, obtained well surface of planeness, and original oxide compound eliminates basically, so this step pickling (mineral acid) is considered whether pickling according to surface condition, and the time is unsuitable long, otherwise can cause the excessive erosion of pickling, thereby influence the bonding force of subsequent coated coating and matrix, if excessive erosion, should adopt absorbent cotton to dip in a small amount of dehydrated alcohol and clean, ultrasonic wave is washed then.
(2) preparation of colloidal sol:
Adopt sol-gel method to prepare single component Al
2O
3(inorganic salt are precursor), MgO (inorganic salt are precursor), SiO
2(organic alkoxide is a precursor), ZrO
2(inorganic salt are precursor), TiO
2The complex sol of (organic alkoxide is a precursor) colloidal sol and certain proportion various combination mode;
(3) coating and thermal treatment:
The base material that pre-treatment is stand-by carries out successively: soak the pool and lift coating colloidal sol coating, airing film forming, thermal treatment, acetone cleaning by degreasing, repeatedly soak the pool and lift coating;
Use dip-coating method that the sintering type Nd iron boron matrix that carries out pre-treatment is applied, obtain sol pellicle, apply different single component colloidal sol thin layers, after airing film forming and the thermal treatment, repeat aforementioned operation repeatedly according to different needs on its surface; Select different single components or plural components colloidal sol repeatedly to apply, with the thickness of control coating, obtain the suitable metal oxide ceramic coating of thickness, in conjunction with high power metallography microscope sem observation, coating is complete, no macroscopic defects;
The different coating array mode of corrosion-resistant gradient different choice according to selecting roughly is divided into three kinds of different applying coatings: the lowest layer, middle layer, outermost layer:
The lowest layer: adopt the single component sol layer, should adopt MgO colloidal sol and SiO
2Colloidal sol applies 2～3 times;
Middle layer: adopt the complex sol coating to apply 2～3 times;
Outermost layer: according to the mode that the performance that applies the internal layer coating is regulated outer coating, can use the single component coating, also can use compound coating, apply 2～3 times, make it to form a kind of sol layer of gradient protection;
The situation that combines of collosol coating and matrix mainly is subjected to the viscosity of colloidal sol and the speed that lifts influences, behind the metal oxide sol ageing certain hour for preparing; when its dissolved adhesiveness is controlled at 1～13mPas, be easy to apply, form protective layer; at room temperature dipping lifts, and dipping 1～3min is with 2 * 10
-3M/s～2 * 10
-4The pull rate of m/s at the uniform velocity lifts out in the sol solutions, and low-temperature heat treatment after the film forming progressively is warmed up to 180 ℃, constant temperature 30～60min, treat after the solvent evaporates to obtain the single layer oxide nanoparticulate thin films, repeat the aforesaid operations process and can obtain the multilayered particles film 4～6 times in 350～800 ℃ of sintering; Film to guarantee that coated surface clean do not have impurity such as grit at every turn, and the even film layer of being hung to guarantee is not broken in drying process; Thermal treatment is as follows:
The lowest layer: dry 0.5 hour film forming in air, at the uniform velocity be warming up to 60 ℃, insulation 0.5h is warming up to 180 ℃ again;
Middle layer: in air, dry 0.5 hour film forming, at the uniform velocity be warming up to 350 ℃;
Outermost layer: in air, dry 0.5 hour film forming, at the uniform velocity be warming up to 500 ℃ of insulation 30min.
(4) coating of metal oxides pre-electroplating treatment:
Carry out degreasing, cold wash, sensitization, activation, cold wash, chemical Ni-P plating, cold wash successively
(5) electroplated Ni-P:
Be coated with the neodymium iron boron matrix of oxide ceramic coating, after pre-electroplating treatment, washed with de-ionized water is put into electroplate liquid and is electroplated, and chargedly goes into groove; Be coated with the neodymium iron boron matrix of oxide ceramic coating, after pre-electroplating treatment, implement electroplating technology, get fine and close, bright coating; The processing condition of electroplate liquid are: NiSO
47H
2O:250～300g/L, NiCl6H
2O:30～50g/L, H
3BO
3: 30～40g/L, sodium lauryl sulphate: 0.05～0.1g/L, 1,4-butynediol: 0.3～0.5g/L, asccharin: 0.6～1.0g/L, complexing agent is an amount of, and the pH value is 5～6, and temperature is 45 ℃～55 ℃, and current density is 1～2.5A/dm
2, electroplating time is 30min.
After electroplate liquid uses for some time, when electroplate liquid muddiness occurs or has floss to occur, need carry out the electroplate liquid activation, add proper amount of active carbon and about 60 ℃, stirred one hour, filter the corresponding electroplating additive of back adding, stir.
Performance Detection is corrosion resisting property and binding force of cladding material experimental result below:
Corrosion resisting property: carry out the erosion resistance experiment according to GB.4334.6-84
Therefore, metal oxide is galvanized has improved nearly more than 400 times than the erosion resistance of not carrying out any coating protection matrix for band, has improved nearly 300 times than the erosion resistance of chemical Ni-P plating activation back electroplated Ni-P.
Binding force of cladding material: adopt the rapid heat cycle method to detect, in retort furnace, be warmed up to 300 ℃, through 8 quenchings, its coating of sample of chemical Ni-P plating re-plating Ni-P has slight wrinkling behind the constant temperature 1h, and the sample of electroplated Ni-P does not have considerable change behind the trilamellar membrane and be coated with; Continue to be warmed up to 400 ℃, behind the constant temperature 1h, the sample of chemical Ni-P plating re-plating Ni-P coating when first time quenching comes off immediately, the sample of electroplated Ni-P does not still have considerable change after through the quenching more than 10 times behind three layers of dissolved glue film and be coated with, and the coating after filming in the time of 600 ℃ of heating up on this basis is oxidized wrinkling, obscission not occur yet.
Advantage of the present invention is, adopt new surface modification treatment means, electroplate the advantage of (or electroless plating) and the characteristics of colloidal sol-gel technique in conjunction with tradition, thereby avoided that coating adhesion is bad in the single coating, compactness is relatively poor, caused easily coming off, have hole and single collosol coating too thin and do not reach the defective of anti-corrosion function.After this method is handled, form fine and close collosol coating at the neodymium iron boron substrate material surface, sintering processes obtains the gel oxide ceramic coating, on gel coat, implement coating then again, form functionally gradient coating, the neodymium iron boron body material is played anticorrosion comprehensively, realize the industrial applications purpose.
Embodiment
Embodiment 1:
Use sintering type Nd iron boron to be material, carry out surface treatment: the preparation of pretreatment of base material → colloidal sol → soak the pool to lift coating oxide sol → coating thermal treatment → pre-electroplating treatment → plating → Performance Detection by the processing scheme of following each step:
(1) pretreatment of base material
Carry out surface finish, degreasing, washing, pickling successively, ultrasonic wave washing back is preserved stand-by in ethanol;
The neodymium iron boron matrix reaches about 7 surfaceness through polishing, then cleans 5min with the electrochemical deoiling ultra-sonic dispersion, and pickling 0.5min in rear surface cleans the back and preserves stand-by in ethanol;
(2) preparation of colloidal sol
The preparation of MgO colloidal sol:
With magnesium nitrate (Mg (NO
3)
26H
2O) be precursor, it is dissolved in the part alcoholic solution (is called A liquid), with the collodion is annex solution, be dissolved in the part alcoholic solution and (be called B liquid), make the mass ratio of inorganic magnesium salt and collodion be controlled at 0.08:1, the volume ratio of control solvent and annex solution is 7:3, heated and stirred A liquid, during backflow B liquid is dropwise joined in the A liquid, continue heated and stirred backflow 30min, promptly get the magnesium oxide colloidal sol of stable transparent;
SiO
2The colloidal sol preparation:
With tetraethoxy (TEOS) is precursor, and dehydrated alcohol and distilled water are solvent, the mol ratio (TEOS:C of control raw material
2H
5OH:H
2O=1:4:4), tetraethoxy is dissolved in the part alcohol liquid (being called A liquid), distilled water is dissolved in the pure liquid of other part and (is called B liquid), and B liquid dropwise joins in the A liquid of continuous stirring, continues to stir 2 hours, can get relatively stable, transparent silicon sol;
ZrO
2The colloidal sol preparation:
With the inorganic salt basic zirconium chloride is precursor, Virahol is a solvent, deionized water and Glacial acetic acid are catalyzer, the mol ratio of control basic zirconium chloride and deionized water is 8:1, basic zirconium chloride after the grinding is dissolved in (A liquid) in part isopropyl alcohol and the deionized water, adds to drip a small amount of Glacial acetic acid (B liquid) in other part deionized water and Virahol, under the room temperature B liquid is dropwise joined in the A liquid, stirred 2 hours, and promptly obtained the ZrO of stable transparent
2Colloidal sol;
TiO
2The colloidal sol preparation:
With the butyl (tetra) titanate is precursor, dehydrated alcohol is a solvent, concentrated hydrochloric acid and Glacial acetic acid are as the stablizer of this reaction and catalyzer, the mol ratio of control butyl (tetra) titanate and water is 1:3, butyl (tetra) titanate is dissolved in part alcohol liquid, and add Glacial acetic acid and each several of concentrated hydrochloric acids (solution A), magnetic force heated and stirred to 50 ℃; Dropwise drip distilled water and pure mixed solution (solution B), the pH value of control solution drips the back and continues to stir 5 hours about 5, can make the TiO of stable transparent
2Colloidal sol;
The preparation of complex sol: with freshly prepd SiO
2, TiO
2And ZrO
2Single component colloidal sol is pressed SiO
2: TiO
2: ZrO
2The ratio of volume ratio 74:21:5 adopts the mode that stirs, drips to mix, and further promptly gets transparent complex sol after the hydrolysis;
(3) coating and thermal treatment
The base material that pre-treatment is stand-by carries out successively: soak the pool and lift coating colloidal sol coating, airing film forming, thermal treatment, acetone cleaning by degreasing, repeatedly soak the pool and lift coating;
Behind the metal oxide sol ageing certain hour for preparing, at room temperature, will soak to blame to lift in above-mentioned colloidal sol through the good metal base of pre-treatment and film, dipping 1～3min be with 2 * 10
-3M/s～2 * 10
-4The pull rate of m/s at the uniform velocity lifts out sol solutions, and low-temperature heat treatment after the film forming progressively is warmed up to 180 ℃, constant temperature 30min treats after the solvent evaporates to obtain the single layer oxide nanoparticulate thin films in 350 ℃ of sintering, repeat aforesaid operations process 4 times, obtain the multilayered particles film;
The lowest layer: adopt component MgO sol layer, apply 2 times;
Middle layer: adopt compound (SiO
2: TiO
2: ZrO
2Volume ratio 74:21:5) collosol coating applies 2 times;
Outermost layer: adopt SiO
2Sol layer applies 3 times;
Thermal treatment:
The lowest layer: dry 0.5 hour film forming in air, at the uniform velocity be warming up to 60 ℃, insulation 0.5h is warming up to 180 ℃ again;
Middle layer: in air, dry 0.5 hour film forming, at the uniform velocity be warming up to 350 ℃;
Outermost layer: in air, dry 0.5 hour film forming, at the uniform velocity be warming up to 500 ℃ of insulation 30min.
(4) pre-electroplating treatment
The degreasing process condition is: acetone adds a small amount of sodium lauryl sulphate, ultrasonic stirring 10min;
The processing condition of sensitizing solution are: SnCl
2.H
2O:2～5g/L, HCl (37%): 2～5ml/L, 1～5min under the room temperature;
The processing condition of activation solution are: PdCl
2: 0.3～0.5g/L, HCl:2～5ml/L, pH:7～9, temperature: 20～40 ℃, time 1min;
The processing condition of chemical nickel-plating liquid are: single nickel salt: 25g/L; Inferior sodium phosphate: 25g/L; Ammonia chloride: 30g/L; Trisodium Citrate: 15g/L; Triethanol ammonium: 100g/L; Trisodium phosphate: 60g/L; Sodium lauryl sulphate: an amount of; Thiocarbamide: an amount of; PH value: 8.5～9.5; Temperature: 40-50 ℃; Time: 30min;
(5) electronickelling phosphorus
Be coated with the neodymium iron boron matrix of oxide ceramic coating, after pre-electroplating treatment, washed with de-ionized water is put into electroplate liquid and is electroplated, and chargedly goes into groove; Be coated with the neodymium iron boron matrix of oxide ceramic coating, after pre-electroplating treatment, implement electroplating technology, get fine and close, bright coating; The processing condition of electroplate liquid are: NiSO
47H
2O:250～300g/L, NiCl
26H
2O:30～50g/L, H
3BO
3: 30～40g/L, sodium lauryl sulphate: 0.05～0.1g/L, 1,4-butynediol: 0.3～0.5g/L, asccharin: 0.6～1.0g/L, complexing agent is an amount of, and the pH value is 5～6, and temperature is 45 ℃～55 ℃, and current density is 1～2.5A/dm
2, electroplating time is 30min.
Performance Detection (sample to be detected is: sol-gel coating add electrolytic coating sample, single sol-gel coating sample, single electrolytic coating sample, do not carry out any coating protection sample)
A: the test of porosity, adopt to post filter paper method
With { K
3[Fe (CN)
6] the impregnated filter paper of 10g/L+NaCl 15g/L+ gelatinum 15g/L} is attached to the specimen surface of cleaning, takes off filter paper behind the 5min, dry back is observed, is calculated the filter paper blueing and counts, and asks porosity, and calculation formula is as follows:
Porosity=N/S is (individual/cm
2)
N represents filter paper Bluepoint number, and S represents the coating face measured.The arithmetical av of three tests is as measurement result.
B: the corrosion of coating test, sea water immersion test, adopt manual simulation's seawater, its prescription following (g/L):
NaCl?26.5；KCl?0.73；NaBr?0.28；CaCl
21.1；MgCl
2?2.4；MgSO
4?3.3；NaHCO
3?0.2
Sample to be detected is immersed in the seawater of new preparation, at interval 2h, 6h, 12h observe the specimen surface changing conditions, begin to occur losing a little time (h) as the solidity to corrosion of coating sample dip test in synthetic sea water with sample.
The result shows: adopt sol-gel coating to add the electrolytic coating technology, coating is finer and close, and raising is clearly arranged on anticorrosion solidity to corrosion.
Embodiment 2:
Use sintering type Nd iron boron to be material, carry out surface treatment by the processing scheme of following each step.The preparation of pretreatment of base material → colloidal sol → soak the pool to lift coating oxide sol → coating thermal treatment → pre-electroplating treatment → plating → Performance Detection:
(1) pretreatment of base material
Carry out surface finish, degreasing, washing, pickling successively, ultrasonic wave washing back is preserved stand-by in ethanol;
The neodymium iron boron matrix reaches about 7 surfaceness through polishing, then cleans 7min with the electrochemical deoiling ultra-sonic dispersion, and pickling 0.5min in rear surface cleans the back and preserves stand-by in ethanol;
(2) preparation of colloidal sol
The preparation of MgO colloidal sol:
With magnesium nitrate (Mg (NO
3)
26H
2O) be precursor, it is dissolved in the part alcoholic solution (is called A liquid), with the collodion is annex solution, be dissolved in the part alcoholic solution and (be called B liquid), make the mass ratio of inorganic magnesium salt and collodion be controlled at 0.08:1, the volume ratio of control solvent and annex solution is 7:3, heated and stirred A liquid, during backflow B liquid is dropwise joined in the A liquid, continues heated and stirred backflow 30min, promptly get the magnesium oxide colloidal sol of stable transparent:
SiO
2The colloidal sol preparation:
With tetraethoxy (TEOS) is precursor, and dehydrated alcohol and distilled water are solvent, the mol ratio (TEOS:C of control raw material
2H
5OH:H
2O=1:4:4), tetraethoxy is dissolved in the part alcohol liquid (being called A liquid), distilled water is dissolved in the pure liquid of other part and (is called B liquid), and B liquid dropwise joins in the A liquid of continuous stirring, continues to stir 2 hours, can get relatively stable, transparent silicon sol.
Al
2O
3The colloidal sol preparation:
With aluminum nitrate [Al (NO
3)
39H
2O] (be mixed with 0.2molL
-1Solution) and six methylene radical tetramine [(CH
2)
6N
4] (be mixed with 1mol.L
-1Solution) be precursor.With deionized water is solvent, under room temperature constantly stirs, add an amount of six methylene radical tetramine solution (mol ratio of aluminum nitrate and six methylene radical tetramines is 1:3) in aluminum nitrate solution, continuation stirring for some time makes vitreosol, adds a spot of stablizer (diethanolamine) at last;
The preparation of complex sol: with freshly prepd SiO
2Press SiO with MgO single component colloidal sol
2: the ratio of MgO volume ratio 7:3, adopt the mode that stirs, drips to mix, further promptly get transparent complex sol after the hydrolysis;
(3) coating and thermal treatment
The base material that pre-treatment is stand-by carries out successively: soak the pool and lift coating colloidal sol coating, airing film forming, thermal treatment, acetone cleaning by degreasing, repeatedly soak the pool and lift coating;
Behind the metal oxide sol ageing certain hour for preparing, at room temperature, will soak to blame to lift in above-mentioned colloidal sol through the good metal base of pre-treatment and film, dipping 1～3min be with 2 * 10
-3M/s～2 * 10
-4The pull rate of m/s at the uniform velocity lifts out sol solutions, and low-temperature heat treatment after the film forming progressively is warmed up to 180 ℃, constant temperature 30min treats after the solvent evaporates to obtain the single layer oxide nanoparticulate thin films in 600 ℃ of sintering, repeat aforesaid operations process 6 times, obtain the multilayered particles film;
The lowest layer: adopt component MgO sol layer, apply 3 times;
Middle layer: adopt compound (SiO
2: collosol coating MgO volume ratio 7:3) applies 2 times;
Outermost layer: adopt Al
2O
3Sol layer applies 2 times.
Thermal treatment:
The lowest layer: dry 0.5 hour film forming in air, at the uniform velocity be warming up to 60 ℃, insulation 0.5h is warming up to 180 ℃ again;
Middle layer: in air, dry 0.5 hour film forming, at the uniform velocity be warming up to 350 ℃;
Outermost layer: in air, dry 0.5 hour film forming, at the uniform velocity be warming up to 500 ℃ of insulation 30min.
(4) pre-electroplating treatment
The degreasing process condition is: acetone adds a small amount of sodium lauryl sulphate, ultrasonic stirring 10min;
The processing condition of sensitizing solution are: SnCl
2.H
2O:2～5g/L, HCl (37%): 2～5ml/L, 1～5min under the room temperature;
The processing condition of activation solution are: PdCl
2: 0.3～0.5g/L, HCl:2～5ml/L, pH:7～9, temperature: 20～40 ℃, time 1min;
The processing condition of chemical nickel-plating liquid are: single nickel salt: 25g/L; Inferior sodium phosphate: 25g/L; Ammonia chloride: 30g/L; Trisodium Citrate: 15g/L; Triethanol ammonium: 100g/L; Trisodium phosphate: 60g/L; Sodium lauryl sulphate: an amount of; Thiocarbamide: an amount of; PH value: 8.5～9.5; Temperature: 40-50 ℃; Time: 30min;
(5) electronickelling phosphorus
Be coated with the neodymium iron boron matrix of oxide ceramic coating, after pre-electroplating treatment, washed with de-ionized water is put into electroplate liquid and is electroplated, and chargedly goes into groove; Be coated with the neodymium iron boron matrix of oxide ceramic coating, after pre-electroplating treatment, implement electroplating technology, get fine and close, bright coating; The processing condition of electroplate liquid are: NiSO
47H
2O:250～300g/L, NiCl
26H
2O:30～50g/L, H
3BO
3: 30～40g/L, sodium lauryl sulphate: 0.05～0.1g/L, 1,4-butynediol: 0.3～0.5g/L, asccharin: 0.6～1.0g/L, complexing agent is an amount of, and the pH value is 5～6, and temperature is 45 ℃～55 ℃, and current density is 1～2.5A/dm
2, electroplating time is 30min.
Performance Detection (sample to be detected is: sol-gel coating add electrolytic coating sample, single sol-gel coating sample, single electrolytic coating sample, do not carry out any coating protection sample)
A: the test of porosity, adopt to post filter paper method
With { K
3[Fe (CN)
6] the impregnated filter paper of 10g/L+NaCl15g/L+ gelatinum 15g/L} is attached to the specimen surface of cleaning, takes off filter paper behind the 5min, dry back is observed, is calculated the filter paper blueing and counts, and asks porosity, and calculation formula is as follows:
Porosity=N/S is (individual/cm
2)
N represents filter paper Bluepoint number, and S represents the coating face measured.The arithmetical av of three tests is as measurement result.
B: corrosion of coating test: 5% sulfuric acid corrosion soak test
Adopt 5% sulfuric acid room temperature soak test, claim sample weight (being accurate to 0.1mg) before and after the test.After the immersion, from testing liquid, take out sample, cleaning, dry, weighing.Each experiment must be used new sample solution.The corrosive nature of sample represents with corrosion rate, i.e. the weightlessness of unit surface, unit time, and unit is g/cm
2H.Corrosion rate is calculated as follows:
Corrosion rate=W
Before-W
After/ St
W
Before---the weight of sample before the expression test, g; W
After---the weight of expression test back sample, g;
S---sample area, cm
2T---test period, h.
The result shows: adopt sol-gel coating to add the electrolytic coating technology, coating is finer and close, and raising is clearly arranged on anticorrosion solidity to corrosion.
Embodiment 3:
Use sintering type Nd iron boron to be material, carry out surface treatment: the preparation of pretreatment of base material → colloidal sol → soak the pool to lift coating oxide sol → coating thermal treatment → pre-electroplating treatment → plating → Performance Detection by the processing scheme of following each step:
(1) pretreatment of base material
Carry out surface finish, degreasing, washing, pickling successively, ultrasonic wave washing back is preserved stand-by in ethanol;
The neodymium iron boron matrix reaches about 7 surfaceness through polishing, then cleans 10min with the electrochemical deoiling ultra-sonic dispersion, and pickling 0.5min in rear surface cleans the back and preserves stand-by in ethanol;
(2) preparation of colloidal sol
SiO
2The colloidal sol preparation:
With tetraethoxy (TEOS) is precursor, and dehydrated alcohol and distilled water are solvent, the mol ratio (TEOS:C of control raw material
2H
5OH:H
2O=1:4:4), tetraethoxy is dissolved in the part alcohol liquid (being called A liquid), distilled water is dissolved in the pure liquid of other part and (is called B liquid), and B liquid dropwise joins in the A liquid of continuous stirring, continues to stir 2 hours, can get relatively stable, transparent silicon sol;
ZrO
2The colloidal sol preparation:
With the inorganic salt basic zirconium chloride is precursor, Virahol is a solvent, deionized water and Glacial acetic acid are catalyzer, the mol ratio of control basic zirconium chloride and deionized water is 8:1, basic zirconium chloride after the grinding is dissolved in (A liquid) in part isopropyl alcohol and the deionized water, adds to drip a small amount of Glacial acetic acid (B liquid) in other part deionized water and Virahol, under the room temperature B liquid is dropwise joined in the A liquid, stirred 2 hours, and promptly obtained the ZrO of stable transparent
2Colloidal sol;
TiO
2The colloidal sol preparation:
With the butyl (tetra) titanate is precursor, dehydrated alcohol is a solvent, concentrated hydrochloric acid and Glacial acetic acid are as the stablizer of this reaction and catalyzer, the mol ratio of control butyl (tetra) titanate and water is 1:3, butyl (tetra) titanate is dissolved in part alcohol liquid, and drip Glacial acetic acid and each several of concentrated hydrochloric acids (solution A), magnetic force heated and stirred to 50 ℃; Dropwise drip distilled water and pure mixed solution (solution B), the pH value of control solution drips the back and continues to stir 5 hours about 5, can make the TiO of stable transparent
2Colloidal sol;
The preparation of complex sol: with freshly prepd SiO
2, TiO
2And ZrO
2Single component colloidal sol is pressed SiO
2: TiO
2: ZrO
2The ratio of volume ratio 73:20:7 adopts the mode that stirs, drips to mix, and further promptly gets transparent complex sol after the hydrolysis;
(3) coating and thermal treatment
The base material that pre-treatment is stand-by carries out successively: soak the pool and lift coating colloidal sol coating, airing film forming, thermal treatment, acetone cleaning by degreasing, repeatedly soak the pool and lift coating;
Behind the metal oxide sol ageing certain hour for preparing, at room temperature, will soak to blame to lift in above-mentioned colloidal sol through the good metal base of pre-treatment and film, dipping 1～3min be with 2 * 10
-3M/s～2 * 10
-4The pull rate of m/s at the uniform velocity lifts out sol solutions, and low-temperature heat treatment after the film forming progressively is warmed up to 180 ℃, constant temperature 30min treats after the solvent evaporates to obtain the single layer oxide nanoparticulate thin films in 800 ℃ of sintering, repeat aforesaid operations process 5 times, obtain the multilayered particles film;
The lowest layer: adopt component S iO
2Sol layer applies 3 times;
Middle layer: adopt compound (SiO
2: TiO
2: ZrO
2Volume ratio 73:20:7) collosol coating applies 2 times;
Outermost layer: adopt SiO
2Sol layer applies 2 times.
Thermal treatment:
The lowest layer: dry 0.5 hour film forming in air, at the uniform velocity be warming up to 60 ℃, insulation 0.5h is warming up to 180 ℃ again;
Middle layer: in air, dry 0.5 hour film forming, at the uniform velocity be warming up to 350 ℃;
Outermost layer: in air, dry 0.5 hour film forming, at the uniform velocity be warming up to 500 ℃ of insulation 30min.
(4) pre-electroplating treatment
The degreasing process condition is: acetone adds a small amount of sodium lauryl sulphate, ultrasonic stirring 10min;
The processing condition of sensitizing solution are: SnCl
2.H
2O:2～5g/L, HCl (37%): 2～5ml/L, 1～5min under the room temperature;
The processing condition of activation solution are: PdCl
2: 0.3～0.5g/L, HCl:2～5ml/L, pH:7～9, temperature: 20～40 ℃, time 1min;
The processing condition of chemical nickel-plating liquid are: single nickel salt: 25g/L; Inferior sodium phosphate: 25g/L; Ammonia chloride: 30g/L; Trisodium Citrate: 15g/L; Triethanol ammonium: 100g/L; Trisodium phosphate: 60g/L; Sodium lauryl sulphate: an amount of; Thiocarbamide: an amount of; PH value: 8.5～9.5; Temperature: 40-50 ℃; Time: 30min;
(5) electronickelling phosphorus
Be coated with the neodymium iron boron matrix of oxide ceramic coating, after pre-electroplating treatment, washed with de-ionized water is put into electroplate liquid and is electroplated, and chargedly goes into groove; Be coated with the neodymium iron boron matrix of oxide ceramic coating, after pre-electroplating treatment, implement electroplating technology, get fine and close, bright coating; The processing condition of electroplate liquid are: NiSO
47H
2O:250～300g/L, NiCl
26H
2O:30～50g/L, H
3BO
3: 30～40g/L, sodium lauryl sulphate: 0.05～0.1g/L, 1,4-butynediol: 0.3～0.5g/L, asccharin: 0.6～1.0g/L, complexing agent is an amount of, and the pH value is 5～6, and temperature is 45 ℃～55 ℃, and current density is 1～2.5A/dm
2, electroplating time is 30min.
Performance Detection (sample to be detected is: sol-gel coating add electrolytic coating sample, single sol-gel coating sample, single electrolytic coating sample, do not carry out any coating protection sample)
A: binding force of cladding material strength trial: thermal shock test; adopt the rapid heat cycle method; with sample to be detected (sol-gel coating add electrolytic coating sample, single sol-gel coating sample, single electrolytic coating sample, do not carry out any coating protection sample) directly put into 200 ℃ of High Temperature Furnaces Heating Apparatuss; heating and insulation; take out after 1 hour and put into room temperature water at once and cool off suddenly; because coating is different with the matrix shrinking percentage, between coating and matrix, can produce an isolating power behind the chilling.Circulation is repeatedly observed coating and body material bonding force intensity, with maximum cycle indexes that defectives such as chapping, peel off do not occur as its heat-shock resistance index.
B: corrosion experiment: adopt the neutral sodium chloride solution soak test, the NaCl solution of preparation 5%, and with 0.1mol/LHCl and 0.1mol/LNaOH solution adjusting pH value to 7, as testing liquid.Under the room temperature, specimen test to be detected is faced up, lie in a horizontal plane in the testing liquid, surface to volume ratio (being the ratio that experimental solutions volume and sample are tested area) is 30mL/cm
2Adopt 3 samples to do parallel laboratory test under the identical conditions.Test to 2h, 6h, 12h, 24h, 48h takes out sample and checks during 96h, come the solidity to corrosion of comparative coatings by two indexs of corrosion rate of specimen test face after beginning the time of visible spot corrosion to occur and testing termination.
The result shows: adopt sol-gel coating to add the electrolytic coating technology, binding force of cladding material is strong, and raising is clearly arranged on anticorrosion solidity to corrosion.
Claims (4)
1. a process for preparing neodymium-iron-boron permanent magnetic material surface gradient function coating layer is characterized in that, realizes through the following steps successively:
(1) pre-treatment of sintered type NdFeB permanent magnet body material:
Carry out successively in ethanol, preserving after surface finish, degreasing, washing, pickling, the ultrasonic wave washing, stand-by;
(2) preparation of colloidal sol:
Adopt sol-gel method to prepare single component Al
2O
3, MgO, SiO
2, ZrO
2, TiO
2The complex sol of colloidal sol and certain proportion various combination mode;
(3) coating and thermal treatment:
The base material that pre-treatment is stand-by carries out successively: dipping lifts coating colloidal sol coating, airing film forming, thermal treatment, acetone cleaning by degreasing, repeatedly dipping lifts coating;
Use dip-coating method that the sintering type Nd iron boron matrix that carries out pre-treatment is applied, obtain sol pellicle, apply different single component colloidal sol thin layers, after airing film forming and the thermal treatment, repeat aforementioned operation repeatedly according to different needs on its surface; Select different single components or plural components colloidal sol repeatedly to apply, with the thickness of control coating, obtain the suitable metal oxide ceramic coating of thickness, in conjunction with high power metallography microscope sem observation, coating is complete, no macroscopic defects;
(4) metal oxide ceramic coating pre-electroplating treatment:
Carry out degreasing, cold wash, sensitization, activation, cold wash, chemical Ni-P plating, cold wash successively;
(5) electroplated Ni-P:
Be coated with the neodymium iron boron matrix of oxide ceramic coating, after pre-electroplating treatment, put into electroplate liquid after the washed with de-ionized water and electroplate, chargedly go into groove, fine and close, bright coating, the processing condition of electroplate liquid are: NiSO
47H
2O:250～300g/L, NiCl
26H
2O:30～50g/L, H
3BO
3: 30～40g/L, sodium lauryl sulphate: 0.05～0.1g/L, 1,4-butynediol: 0.3～0.5g/L, asccharin: 0.6～1.0g/L, complexing agent is an amount of, and the pH value is 5～6, and temperature is 45 ℃～55 ℃, and current density is 1～2.5A/dm
2, electroplating time is 30min.
2. method according to claim 1 is characterized in that, in the step (1), surface finish is according to processed features of shape, adopts sandblast, barreling, mechanical polishing or grinding, and making surfaceness is 7; The degreasing Recipe is: NaOH:60g/L; Na
3PO
412H
2O:15g/L; Room temperature; 10min; Add an amount of tensio-active agent sodium lauryl sulphate, ultrasonic agitation is cleaned.
3. method according to claim 1 is characterized in that, in the step (3), according to three kinds of different applying coatings of corrosion-resistant gradient different choice of selecting: the lowest layer, middle layer, outermost layer;
The lowest layer: adopt the single component sol layer, MgO colloidal sol and SiO
2Colloidal sol applies 2～3 times;
Middle layer: adopt the complex sol coating to apply 2～3 times;
Outermost layer: according to the mode that the performance that applies the internal layer coating is regulated outer coating, use single component coating or compound coating, apply 2～3 times, make it to form a kind of sol layer of gradient protection;
Behind the metal oxide sol ageing certain hour for preparing, when its dissolved adhesiveness is controlled at 1～13mPas, be easy to apply, form protective layer, at room temperature dipping lifts, and dipping 1～3min is with 2 * 10
-3M/s～2 * 10
-4The pull rate of m/s at the uniform velocity lifts out in the sol solutions, and low-temperature heat treatment after the film forming progressively is warmed up to 180 ℃, constant temperature 30～60min, treat after the solvent evaporates to obtain the single layer oxide nanoparticulate thin films, repeat the aforesaid operations process and obtain the multilayered particles film 4～6 times in 350～800 ℃ of sintering; Film to guarantee that coated surface clean do not have grit impurity at every turn, and the even film layer of being hung to guarantee is not broken in drying process; Thermal treatment is as follows:
The lowest layer: dry 0.5 hour film forming in air, at the uniform velocity be warming up to 60 ℃, insulation 0.5h is warming up to 180 ℃ again;
Middle layer: in air, dry 0.5 hour film forming, at the uniform velocity be warming up to 350 ℃;
Outermost layer: in air, dry 0.5 hour film forming, at the uniform velocity be warming up to 500 ℃ of insulation 30min.
4. method according to claim 1 is characterized in that, in the step (4), processing condition are:
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| CN112007781A (en) | 2020-09-07 | 2020-12-01 | 烟台首钢磁性材料股份有限公司 | Preparation device and preparation method of neodymium iron boron permanent magnet ceramic coating |
| CN113005440A (en) * | 2020-12-30 | 2021-06-22 | 昆明狴犴人力资源服务有限公司 | Neodymium-iron-boron permanent magnet surface coating and preparation method thereof |
| CN112992521B (en) * | 2021-03-09 | 2023-03-17 | 合肥工业大学 | Preparation method of low-weight-loss sintered NdFeB magnet |
| CN115505982A (en) * | 2022-08-23 | 2022-12-23 | 浙江英洛华磁业有限公司 | Zinc-nickel alloy coating on surface of sintered neodymium-iron-boron material and electroplating process thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164436A (en) * | 1996-05-08 | 1997-11-12 | 中国科学院大连化学物理研究所 | Method for preparation of extra-thin palladium-ceramic compound film |
| JP2001135511A (en) * | 1999-11-09 | 2001-05-18 | Sumitomo Special Metals Co Ltd | Microminiature magnet excellent in anticorrosion |
| US6344242B1 (en) * | 1999-09-10 | 2002-02-05 | Mcdonnell Douglas Corporation | Sol-gel catalyst for electroless plating |
-
2006
- 2006-07-14 CN CNB2006100544400A patent/CN100464007C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164436A (en) * | 1996-05-08 | 1997-11-12 | 中国科学院大连化学物理研究所 | Method for preparation of extra-thin palladium-ceramic compound film |
| US6344242B1 (en) * | 1999-09-10 | 2002-02-05 | Mcdonnell Douglas Corporation | Sol-gel catalyst for electroless plating |
| JP2001135511A (en) * | 1999-11-09 | 2001-05-18 | Sumitomo Special Metals Co Ltd | Microminiature magnet excellent in anticorrosion |
Non-Patent Citations (4)
| Title |
|---|
| Preparation and corrosion resistance of NiP/TiO2compositefilm on carbon steel in sulfuric ACID solution. L.Z.Song, S.Z.Song, J.Zhao.Acta Metall.Sin. (Engl. Lett.),Vol.19 No.2. 2006 |
| Preparation and corrosion resistance of NiP/TiO2compositefilm on carbon steel in sulfuric ACID solution. L.Z.Song, S.Z.Song, J.Zhao.Acta Metall.Sin. (Engl. Lett.),Vol.19 No.2. 2006 * |
| 金属陶瓷涂层耐蚀性能研究. 李青，陈艳.材料保护，第33卷第5期. 2000 |
| 金属陶瓷涂层耐蚀性能研究. 李青，陈艳.材料保护，第33卷第5期. 2000 * |
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