Summary of the invention
The present invention finishes according to above-mentioned main points.According to a first aspect of the invention and feature, a kind of method of making erosion-resisting rare earth based permanent magnet is provided, it is characterized in that described method comprises provides a kind of aqueous treatment, it comprises the hydrolytic polymerization product of alkyl silicate and the thin zinc particle that average grain diameter is 1 to 50 micron, and the pH value be 6 to 8 and viscosity be 1000cP or littler; On the surface of rare earth base permanent magnet, use treatment fluid, and make the gained permanent magnet under 400 ℃, accept heat treatment, thereby form the anticorrosive film that has wherein disperseed thin zinc particle at 250 ℃.
Except first feature, according to a second aspect of the invention and feature, thin zinc particle is a sheet-like particle.
Except first feature, according to a third aspect of the present invention and feature, the total content of alkyl silicate raw material in the aqueous treatment and thin zinc particle has occupied 40% weight to 90% weight, and (wherein alkyl silicate content changes into SiO
2Content).
Except first feature, according to a fourth aspect of the present invention and feature, the mixing ratio of alkyl silicate raw material in the aqueous treatment and thin zinc particle is that (weight ratio: wherein alkyl silicate content changed into SiO in 1: 1 to 1: 19
2Content).
Except first feature, according to a fifth aspect of the present invention and feature, in aqueous treatment, add organic dispersing agent.
Except first feature, according to a sixth aspect of the invention and feature, the thickness that has wherein disperseed the anticorrosive film of thin zinc particle is 1 micron to 50 microns.
Except first feature, according to a seventh aspect of the present invention and feature, disperseed the additional thin inorganic particle that disperses other in the anticorrosive film of thin zinc particle therein.
Except first feature, according to an eighth aspect of the present invention and feature, by the surface applied aqueous treatment of dipping spin coating method to rare earth based permanent magnet.
Except the 8th feature, according to a ninth aspect of the present invention and feature, implement described method as the aqueous treatment of 300cP to 600cP by using viscosity.
Except the 8th feature, according to a tenth aspect of the present invention and feature, following enforcement dipping spin coating method: a plurality of rare earth based permanent magnets are supported on about form peripheral edge portions of the turntable that can rotate around vertical center axis as rotating shaft, by using aqueous treatment dip-coating rare earth based permanent magnet in the turntable immersion aqueous treatment flow container that has rare earth based permanent magnet above inciting somebody to action, from treatment fluid, take out the turntable of gained then, revolving-turret is removed the excessive aqueous treatment that adheres on the rare earth based permanent magnet with centrifugation.
Except the tenth feature, according to an eleventh aspect of the present invention and feature, a plurality of rare earth based permanent magnets are supported on about form peripheral edge portions of turntable with the layout that is approximately ring-type.
Except the tenth feature, according to a twelfth aspect of the present invention and feature, rare earth based permanent magnet is slim magnet.
Except the 12 feature,, place slim magnet in the wideest mode about and the turntable radial parallel of slim magnet according to the 13 aspect of the present invention and feature.
Except the 13 feature, according to the 14 aspect of the present invention and feature, following use coating anchor clamps: in the situation that places it in the about form peripheral edge portions of turntable, each slim magnet is separated from each other, and its wideest approximately and the radial parallel of turntable and layout approximately circlewise.
Except the 12 feature, according to the 15 aspect of the present invention and feature, the shape of slim magnet is selected from plane, ring-type and arcuation shape.
Except the 14 feature, according to the 16 aspect of the present invention and feature, at dipping after spin coating finishes, separately apply anchor clamps and slim magnet still is fixed in the above, and the slim magnet that still is fixed on above the coating anchor clamps is accepted heat treatment in place arbitrarily.
According to the 17 aspect of the present invention and feature, a kind of rare earth based permanent magnet is provided, has it is characterized by and have on its surface that to have disperseed average grain diameter at alkyl silicate in as raw-material film composition be the anticorrosive film of 1 micron to 50 microns thin zinc particle.
Except the 17 feature, according to the 18 aspect of the present invention and feature, anticorrosive film comprises the thin zinc particle of 50% weight to 95% weight.
Except the 17 feature, according to nineteen of the present invention aspect and feature, zinc from the diffusion into the surface of magnet to inside.
Except the 17 feature, according to the 20 aspect of the present invention and feature, permanent magnet is by the method manufacturing according to first feature.
According to the 21 aspect of the present invention and feature, a kind of dipping spin coating method that is used for workpiece is provided, it is characterized in that described method comprises a plurality of workpiece support on about form peripheral edge portions of the turntable that can rotate around the vertical center axis as rotating shaft, by using the coating dip coating workpiece in the turntable immersion paint can that has workpiece above inciting somebody to action, from coating, take out the turntable of gained then, revolving-turret is removed the excessive coating that adheres on the workpiece with centrifugation.
According to the 22 aspect of the present invention and feature, a kind of method that forms coated film on workpiece is provided, it is characterized in that described method comprises following use coating anchor clamps: in the situation of the about form peripheral edge portions that places it in the turntable that can rotate around vertical center axis as rotating shaft, each workpiece is separated from each other, roughly layout circlewise; And it further comprises by using the coating dip coating workpiece in the turntable immersion paint can that has the coating anchor clamps of having fixed workpiece above inciting somebody to action, from coating, take out the turntable and the revolving-turret of gained, remove the excessive coating that adheres on the workpiece with centrifugation, take off the coating anchor clamps that still are fixed with workpiece from turntable; And if desired, make the workpiece that still is fixed on above the coating anchor clamps accept dried in any place.
Therefore, according to the present invention, provide a kind of stable and simple method to make the rare earth based permanent magnet that has the anticorrosive film that has wherein disperseed thin zinc particle in its surface; Corrosion-resistant rare earth based permanent magnet by described method manufacturing; Be suitable on difform slim workpiece, forming the dipping spin coating method of coated film; And the method that on workpiece, forms coated film.
Embodiment
In the present invention, by on the surface of rare earth based permanent magnet, using the thin zinc particle that the hydrolytic polymerization product that comprises alkyl silicate and average grain diameter are 1 to 50 micron, and the pH value be 6 to 8 and viscosity be 1000cP or littler aqueous treatment, then make the gained permanent magnet under 400 ℃, accept heat treatment then, thereby form the anticorrosive film of the thin zinc particle that wherein comprises dispersion at 250 ℃.The anticorrosive film of the thin zinc particle that wherein comprises dispersion of Xing Chenging has not only been given the highly corrosion performance to rare earth based permanent magnet thus, and has high adhesion strength because zinc inwardly spreads from the surface of magnet.
Alkyl silicate used herein is by general formula: Si
nO
(n-1)(OR)
(2n+2)Express.In the formula, R represents alkyl, for example has the low alkyl group of 1 to 4 carbon atom, as methyl, ethyl, propyl group, butyl etc., but wherein preferably ethyl (be silester, because it is not only cheap, and nontoxic and have a superior working properties.In addition, n represents 1 or bigger integer, but in order to form fine and close film, and n preferably 10 or littler integer.
In addition, the use average grain diameter is 1 to 50 micron a thin zinc particle.This is because if average grain diameter, I'm afraid that thin zinc particle can experience secondary and assemble less than 1 micron in aqueous treatment; On the other hand, if average grain diameter, I'm afraid that thin zinc particle can precipitate greater than 50 microns in aqueous treatment; In any situation, probably all can comprise homodisperse thin zinc particle and have the stable aqueous treatment of excellent deposit and bring difficulty to preparation.The average grain diameter of thin zinc particle is preferably 2 to 30 microns, and more preferably 5 to 20 microns.Thin zinc particle can be an Any shape, but should make the hole that produces in the anticorrosive film of the thin zinc particle that comprises dispersion therein minimum, if thin zinc particle is by lamination densely and to be filled in the film composition be favourable; In addition, being diffused into inside in order to make zinc from magnet surface, is favourable if thin zinc particle has bigger contact area with respect to magnet.Therefore, from the point of view, thin zinc particle is sheet-like particle preferably.At thin zinc particle is under the situation of sheet-like particle, and average grain diameter means average big diameter.
The total content of raw-material alkyl silicate of the conduct in the aqueous treatment and thin zinc particle is preferably 40% weight to 90% weight, and (wherein alkyl silicate content changes into SiO
2Content), 60% weight to 80% weight and more preferably.If total content is lower than 40% weight, I'm afraid that total processing step will increase to the required step more than the anticorrosive film of the thin zinc particle that wherein comprises dispersion with the thickness acquisition that can show enough character; On the other hand, if total content is higher than 90% weight, probably will influence the deposit stability of aqueous treatment.
Be that (weight ratio: wherein alkyl silicate content changed into SiO in 1: 1 to 1: 19 as the mixing ratio of raw-material alkyl silicate and thin zinc particle in the aqueous treatment
2Content), and more preferably 1: 3 to 1: 10, to such an extent as to the content of thin zinc particle will occupy 50% weight to 95% weight of the anticorrosive film of the thin zinc particle that wherein comprises dispersion.Be lower than 50% weight if wherein comprise the content of thin zinc particle in the anticorrosive film of thin zinc particle of dispersion at gained, probably be not enough to show the effect that in film composition, disperses thin zinc particle; On the other hand, if its content is higher than 95% weight, probably can show fully and use the main character of alkyl silicate as raw-material anticorrosive film.
Be limited in 6 to 8 scope to the pH value of the aqueous treatment of rare earth based permanent magnet surface applied,,, probably can cause the corrosion of rare earth based permanent magnet as in the above described in the patent documentation 2 because if the pH value is lower than 6; On the other hand, if the pH value is higher than 8,, probably can not form the anticorrosive film of the thin zinc particle that wherein comprises dispersion with high-adhesion as in the above described in the patent documentation 1.
Viscosity to the aqueous treatment of rare earth based permanent magnet surface applied is limited in 1000cP or lower, because if the viscosity of aqueous treatment surpasses 1000cP, probably be difficult to form the anticorrosive film that has wherein disperseed thin zinc particle and had homogeneous film thickness.
For instance, preferably be prepared by the following method and have excellent inhomogeneity aqueous treatment: with average grain diameter is that 1 micron to 50 microns thin zinc particle joins by alkyl silicate at acid condition (pH value about 3 to 4) or in alkali condition (pH value about 10 to the 12) aqueous solution that hydrolytic-polymeric reaction obtains down, adjusting pH value is 6 to 8 scope, and keep or regulate viscosity to 1000cP or lower (more preferably viscosity is 50cP or lower, more preferably 25cP or lower).In acid condition is hydrolyzed the situation of polymerization reaction, for example regulate the pH value at alkyl silicate by using NaOH to wait.In alkali condition is hydrolyzed the situation of polymerization reaction, for example regulate the pH value at alkyl silicate by using hydrochloric acid to wait.
In order to form fine and close film, alkyl silicate is in the stage of the preparation aqueous treatment polymerization reaction that is hydrolyzed.The hydrolytic-polymeric reaction of alkyl silicate needs not to be carries out the complete hydrolysis polymerization reaction to whole alkyl silicates, but the hydrolytic-polymeric reaction of part alkyl silicate experience is just enough.The acid of adding by control or the consumption of alkali perhaps are controlled at the degree that the consumption of implementing to be used as in the hydrolytic-polymeric reaction water of medium is regulated hydrolytic-polymeric reaction.If the hydrolytic-polymeric reaction degree height of alkyl silicate, the viscosity that aqueous treatment may occur surpasses the situation of 100cP.Even if in case when surpassing the situation of 100cP, can reduce its viscosity by adding warm water etc. in viscosity; But in order to realize the more aqueous treatment of high uniformity, during the hydrolytic-polymeric reaction, trend towards surpassing in the situation of 100cP in the viscosity of aqueous treatment, the adequate measure of preferably taking for example to add water etc. prevents that viscosity from surpassing 100cP.In addition, in the surface tension that needs the control aqueous treatment for the film of easier formation required film thickness is in the situation such as appropriate value, for instance, adding cellulose base thickener (for example water-soluble cellulose ether, as hydroxyethylcellulose, methylcellulose, methylhydroxypropylcellulose, ethylhydroxyethylcellulose, the first and second basic celluloses etc.) in aqueous treatment waits and regulates its viscosity.For thickness of increasing the film that will form etc. and the viscosity that aqueous treatment need be set is in 100cP or the higher situation, preferably in the aqueous treatment for preparing, add thickener, increase its viscosity.
In the aqueous solution that the polymerization reaction that is hydrolyzed to alkyl silicate obtains, add in the situation of thin zinc particle, preferably use organic dispersing agent in aqueous treatment, to disperse thin zinc particle equably.For instance, can in aqueous treatment, add organic dispersing agent by the following method: in the water that has added organic dispersing agent, supply with thin zinc particle, thereby preparation has wherein evenly disperseed the water-bearing media of thin zinc Dispersion of Particles of thin zinc particle, the be hydrolyzed aqueous solution of polymerization reaction acquisition of the water-bearing media that mixes thin zinc Dispersion of Particles then and alkyl silicate.As organic dispersing agent, from with the tack and the cost consideration of thin zinc particle, preferred ionic dispersant (for example aliphatic polycarboxylic acid, polyether polyester carboxylate, macromolecule polyester acid polyamines salt high-molecular polycarboxylic acid long-chain amine etc.), nonionic dispersant (for example carboxylate of polyoxyethylene alkyl ether, the sulfonate of using, perhaps ammonium salt, or sorbitan ester etc.), macromolecule dispersing agent (for example soluble epoxide, the carboxylate of styrene-propene acid copolymer, sulfonate, perhaps ammonium salt, adhesive etc.).
In addition, in order to form the anticorrosive film that has wherein disperseed thin zinc particle of the thickness that can show enough high character and need not excessively repeat manufacturing process, the viscosity of the aqueous treatment of using on the rare earth based permanent magnet surface is preferably 5cP or higher.
When on the rare earth based permanent magnet surface, using aqueous treatment, can use dip-coating method, spraying method, spin coating method, dipping spin coating method etc.In addition, in order to improve the adhesion strength of the anticorrosive film that has wherein disperseed thin zinc particle that on the rare earth based permanent magnet surface, forms, before applying aqueous treatment upward, can be to the surface applied blasting treatment or the pickling processes of magnet.
In order to form inhomogeneity aqueous treatment coated film, preferably on the rare earth based permanent magnet surface, use aqueous treatment by the dipping spin coating method with further improvement.Especially preferably implement the dipping spin coating by the following method: a plurality of rare earth based permanent magnets are supported on about form peripheral edge portions of the turntable that can rotate around vertical center axis as rotating shaft; By using aqueous treatment dip-coating rare earth based permanent magnet in the turntable immersion aqueous treatment flow container that has rare earth based permanent magnet above inciting somebody to action; Take out the turntable of gained then from treatment fluid, centrifugal revolving-turret is removed the excessive aqueous treatment that adheres on the rare earth based permanent magnet.
As on the surface of slim workpiece, forming the method that thickness for example is about 10 microns scumbling tunic, sometimes use the dipping spin coating method, it comprises: use the coating dip coating workpiece in the paint can by workpiece is immersed, from coating, take out the gained workpiece then, high speed rotating is removed the excessive coating that adheres on the workpiece.As the dipping spin coating method that is used for slim workpiece well known in the art, for example may mention the method that Japanese Patent Laid discloses No. 201088/1995 suggestion with diaphragm coating CD.This method comprises: with predetermined space a plurality of substrates of vertical placement on horizontal driving shaft; Except middle body, substrate is immersed in the diaphragm material, simultaneously around the driving shaft low speed rotation, thereby use the material coated substrate; From material, take out products obtained therefrom, by the high speed rotating cutting material.In addition, disclose in Japanese Patent Laid and to have advised a kind of dipping spin coating method in No. 86271/1991, it is characterized by and comprise the centrifugal step of removing coating, coating is applied to as follows to be in by suspension and props up on the object to be applied of the state of carrying: coating plane (tabular surface) approximately becomes horizontal positioned, rotates around the rotating shaft of perpendicular by whole object center of gravity comprising the whole object of suspension and object to be applied.In addition, advised a kind of method of using chip carrier in open 2000-164556 number of Japanese Patent Laid, the face with each other mode of placing of the fluted side of wherein above mask is fixed the supporting member that has groove above a pair of; Wafer by chip carrier towards the supporting of the periphery of groove, and by with groove approximately towards the mode rotating carrier of rotation acceleration direction, thereby from a plurality of wafers that are bearing on the carrier the centrifugal liquid of removing, and dry.
In situation, no matter the shape of workpiece how, preferably realizes applying and can not causing uniformly the fluctuation of thickness to all workpiece to a large amount of slim workpiece use dipping spin coating methods.But according to these situations, all methods of describing in above-mentioned patent documentation all have shortcoming.More particularly, Japanese Patent Laid discloses in No. 201088/1995 the method for describing need keep workpiece by middle body, so this method is owing to be only applicable to annular work piece but imperfect.In addition, described method comprises the frictional force that produces by the horizontal driving shaft that drives with annular work piece interior periphery plane contact and comes rotational workpieces self; Therefore described method has following shortcoming: if the fluctuation of the frictional force between workpiece and the driving shaft, the speed of rotation of workpiece fluctuates, and therefore probably can not realize the even coating of all workpiece.In addition, because be difficult to the high speed rotating workpiece, so described method also suffers another shortcoming,, can not fully remove the coating of excessive adhesion to such an extent as on surface of the work, using in the have high viscosity coating situation of (for example having coating) above 500cP viscosity.In addition, disclose in the method for No. 86271/1991 description, approximately flatly keep workpiece planarization in Japanese Patent Laid; Therefore, owing to probably can cause the difference that adheres to the coating content on plane and the lower plane, this method is imperfect.In addition, in the method for the open 2000-164556 number description of Japanese Patent Laid, with a plane and rotating shaft mode holding workpieces staggered relatively; Therefore according to the position that keeps, rotary speed is different for each workpiece.Therefore, this method has and can not realize the evenly shortcoming of coating to all workpiece.
But the dipping spin coating method of advising among the present invention can be made the uniform coating film and the fluctuation that can not produce thickness on a large scale on slim workpiece.
Explain the dipping spin coating method of advising among the present invention with reference to accompanying drawing when needing, but be to be understood that the dipping spin coating method of advising among the present invention determines without limits in following explanation.The dipping spin coating method of advising among the present invention goes for applying the workpiece of Any shape, no matter the shape of workpiece how, but it is particularly suitable for the slim workpiece of plane, ring-type and arcuation shape.Therefore, in the following description, select method of the present invention is applied to the situation of flat work pieces and annular work piece coating as embodiment.
Fig. 1 is the schematic process flow diagram of the expression example of dipping spin coating method of advising among the present invention.Progressively describe this technology below: (a) at first, a plurality of flat work pieces X are propped up on the about form peripheral edge portions that is loaded in the turntable 2 that can rotate around the vertical center axis 1 as rotating shaft; Wherein place each workpiece X, its wideest (smooth face) approximately is placed to and the radial parallel of turntable 2 and layout approximately circlewise.(b) then, by using cylinder 3 rising paint cans 4, and the method that immerses in the paint cans 4 by the turntable 2 that will top have carried workpiece X, usefulness coating dip coating workpiece X.(c) subsequently, from be coated with feed liquid, take out turntable 2 by using cylinder 3 to reduce paint can 4.(d) last, by using motor 5, thereby centrifugally remove the excessive lip-deep coating of workpiece X that adheres to around the axis of centres 1 revolving-turret 2 (preferred direction of rotation is inverted once at least) as rotating shaft.According to described method, even in the situation of the coating that uses viscosity higher (for example having coating), freely control the coating content that adheres on the workpiece X tabular surface by size or the control rotating speed of regulating turntable 2 above 200cP viscosity; Therefore, can freely control the thickness of coated film.
Preferably, use the plane of mesh plane, to such an extent as to residual coating can not form the coating storage at as turntable 2.
Fig. 2 (a) expression approximately is loaded in the oblique view of the schematic diagram part of the example of state on turntable 2 form peripheral edge portions with the layout of about ring-type with a plurality of flat work pieces X, and wherein the tabular surface of each workpiece X is placed with roughly and radial parallel.Prop up the upper plane figure of the turntable 2 that has carried workpiece X above Fig. 2 (b) expression.(preferably they are bar-shaped and have semicircular cross section) on two supporting members 11 that provide on the turntable 2 is provided workpiece X.As shown in Figure 1, workpiece X can be directly mounted on the turntable 2, and by using this installation method, can be minimized in the installation vestige (referring to Fig. 2 (c)) that produces on the workpiece X lower plane.
By the dividing plate 12 that provides on the direction vertical with respect to supporting member 11 is provided, props up with the state that is separated from each other and carry a flat work pieces X.Dividing plate 12 plays a part also to prevent that workpiece X from rolling.The thickness of workpiece X preferably is wider than at interval between dividing plate 12 and the adjacent separator 12; Because if dividing plate 12 often contacts with the two sides of workpiece X, the contact vestige becomes remarkable.In addition, because can minimize the contact vestige that produces by revolving-turret 2 on the workpiece tabular surface, the cross section of dividing plate 12 is preferably circular.
With reference to processing step (d), by using motor 5 around centrifugal removing in the excessive situation that adheres to the coating on the workpiece X tabular surface as the axis of centres 1 revolving-turret 2 of rotating shaft, because centrifugal force workpiece X trends towards flying to radial direction, but centrifugal adjusting rod 13 and the workpiece X outside plane contact and play a part to suppress workpiece X and fly out of flying out that is fixed on the turntable 2 and arranges in the horizontal direction by abridged member among the figure to direction radially.In addition, centrifugal remove coating during play a part regulate workpiece X motion at the dividing plate 14 that provides on the rotating shaft direction at it with respect to the centrifugal adjusting rod 13 that flies out.
Fig. 3 (a) expression approximately is loaded in the oblique view of the schematic diagram part of the example of state on turntable 2 form peripheral edge portions with the layout of about ring-type with a plurality of annular work piece Y, and wherein the tabular surface of each workpiece Y is placed with roughly and radial parallel.Assign to by abridged member among the figure by the ring portion that hangs workpiece Y and to be fixed on the horizontal hanger components 15 on the turntable 2 to 2 years workpiece Y of turntable.Horizontal hanger components 15 preferably has the bar-like member of circular cross section.In addition, horizontal hanger components 15 parts that preferably will hang workpiece Y cut into for example V-arrangement (referring to Fig. 3 (b)).By using this horizontal hanger components 15 structures, can be minimized in the suspension vestige that workpiece Y loop section produces.
In situation from the dipping spin coating to a plurality of slim workpiece that use, each slim workpiece can directly be propped up and is loaded on the turntable, as shown in Figures 1 to 3; But, in situation about it approximately being placed on the turntable form peripheral edge portions, can use each slim workpiece is separated from each other and make its wideest approximately with turntable radial parallel and about coating anchor clamps of layout circlewise.
Fig. 4 is illustrated in the situation about approximately being placed on the turntable form peripheral edge portions, each slim workpiece is separated from each other and make its wideest approximately with turntable radial parallel and about signal oblique view of an example of coating anchor clamps of layout circlewise.Coating anchor clamps Z comprises two year rods 21 that has dividing plate 22 at least, their quilts and horizontal direction parallel arrangement, and be used for propping up year a plurality of flat work pieces X that are separated from each other, and it is parallel with vertical direction that its tabular surface approximately is placed to, also comprise the centrifugal adjusting rod 23 that flies out that has dividing plate 24, they be placed with horizontal direction parallel and with the outside plane contact of workpiece X, and the anchor clamps of having placed workpiece X in the above are attached on the about form peripheral edge portions of turntable and the situation of turntable rotation in, play a part to suppress workpiece X because centrifugal force flies out to direction radially; But, can also comprise two stick-shaped element 25 that have dividing plate 26 at a upper side of year rod 21, a described stick-shaped element and year rod 21 a parallel placement, it is approximately parallel with vertical direction and keep proper spacing therebetween to make that a plurality of workpiece X can keep tabular surface, and in the situation that anchor clamps are overturn, can keep the top of workpiece X and the described interval between year rod 21 downwards.In the situation that anchor clamps are overturn, keep year rod 21 of workpiece X to play a part stick-shaped element 25 on last stage downwards.
Be fixed with above Fig. 5 represents a plurality of slim workpiece X coating anchor clamps Z front view (a) and along the cutaway view of line D-D (b).
Each preferably has circular cross section to carry rod 21 and stick-shaped element 25.Under this mode, can be minimized in the installation vestige that produces on the slim workpiece X lower plane.In addition, the centrifugal adjusting rod 23 that flies out preferably has circular cross section.Under this mode, can be minimized in the contact vestige that produces on the outer side plane of slim workpiece X.In addition, dividing plate 22, dividing plate 24 and dividing plate 26 each all preferably have circular cross section.Under this mode, can be minimized in the contact vestige that produces on the slim workpiece X tabular surface.In addition, a year rod 21 and stick-shaped element 25 do not need each to form by two, and can each only form by one.
For instance, can following use coating anchor clamps Z shown in Figure 4.Fig. 6 is that expression uses the known fixture that can freely dismantle the top coating anchor clamps Z that has fixed a plurality of flat work pieces X to be attached to the schematic diagram of a part of plan view of situation example on turntable 2 about form peripheral edge portions.According to the flow chart of signal process shown in Figure 1,, promptly use cylinder 3 rising paint cans 4 and with coating dip coating workpiece X by the top attached turntable 2 that is fixed with the coating anchor clamps Z of workpiece X on it is immersed in the paint cans 4.Then, use cylinder 3 to reduce paint can 4, from liquid, take out turntable 2.At last, finish the dipping spin coating around the axis of centres 1 revolving-turret 2, thereby centrifugally remove the excessive coating that adheres on the workpiece X tabular surface as rotating shaft by using motor 5.After having crossed random time, above turntable 2 takes off, fixed the coating anchor clamps Z of workpiece X, and if desired, still be fixed on the last workpiece X of coating anchor clamps Z and accept dried (air dry or heated drying) in any place.Then, the coating anchor clamps Z that has fixed workpiece X is above turned over downwards and is attached to once more on the turntable 2, to such an extent as to implement to flood spin coating with above-mentioned similar methods.In the case, for the second time installation vestige that produces in the coating and the position that contact vestige may be different with the position that produces in coating for the first time, and can in coating for the second time, be coated in apply for the first time in generation the installation vestige with contact vestige; Therefore, can on workpiece X, use more uniform coating.Therefore, above turntable 2 takes off, still fixed the coating anchor clamps Z of workpiece X, and if desired, still be fixed on the last workpiece X of coating anchor clamps Z and accept dried (air dry or heated drying) in any place; In the case, can on a large amount of workpiece, form uniform coated film efficiently and can not cause the fluctuation of thickness.
In addition, when on the rare earth based permanent magnet surface, applying aqueous treatment, can form more uniform coated film as the aqueous treatment of 300cP to 600cP by using viscosity by the dipping spin coating method.Preferably as mentioned above, the aqueous treatment with this viscosity is to have by add the cellulose base thickener in the aqueous treatment for preparing to have increased the treatment fluid of its viscosity (preferably adding thickener with the amount that accounts for aqueous treatment 1% weight to 2% weight).
250 ℃ to the 400 ℃ heat treatments of implementing to be formed with on its surface the rare earth based permanent magnet of aqueous treatment coated film down.By under described temperature conditions, implementing heat treatment, the parts of fine zinc particle that comprises in the aqueous treatment during film forming process suitably from the diffusion into the surface of magnet to inside, and can form the anticorrosive film that has wherein disperseed thin zinc particle of high adhesion strength.If heat treated temperature is lower than 250 ℃, not enough zinc diffusion not only takes place, and water remains on the surface of rare earth based permanent magnet, can fully not evaporate, and therefore probably these water can corrode magnet; On the other hand, if heat treatment temperature is higher than 400 ℃, I'm afraid the diffusion of excessive generation zinc, thereby magnetic is caused adverse influence.For instance, heat treatment period is preferably 10 minutes to 120 minutes.By implemented under 100 ℃ to 170 ℃ predrying after, to its surface applied implement heat treatment on the rare earth based permanent magnet of aqueous treatment coating and can form the more uniform anticorrosive film that has wherein disperseed thin zinc particle.
Preferably drop on 1 micron to 50 micrometer ranges, and, form the anticorrosive film that has wherein disperseed thin zinc particle more preferably 5 microns modes to 15 micrometer ranges with thickness.If thickness less than 1 micron, probably can not fully show the required character of the anticorrosive film that has wherein disperseed thin zinc particle; On the other hand, if thickness surpasses 50 microns, probably can not fully obtain the effective volume of rare earth based permanent magnet.
In addition, disperseed therein can add the thin inorganic particle that disperses other in the anticorrosive film of thin zinc particle.As thin inorganic particle, can mention the low metal of the chemical potential similar, for example the fine particle of aluminium, tin, manganese, magnesium, titanium, nickel etc. to zinc.By disperseing thin alumina particles, can effectively prevent the generation of the white rust (alkaline carbonic acid zinc) that causes owing to thin zinc particle erosion for instance with thin zinc particle.In addition, in order further to reduce the corrosion resistance that the hole that produces in the film also further improves film, can in film, disperse thin oxide particle, for example Al with thin zinc particle
2O
3, TiO
2, SiO
2, mica etc.Disperse together in the situation of thin inorganic particle at thin zinc particle, the total weight of thin zinc particle and thin inorganic particle accounts for 95% weight of the anticorrosive film that forms or still less.
As rare earth based permanent magnet, can mention known R-Fe-B base permanent magnet for instance, perhaps by the R-Fe-N base permanent magnet of Sm-Fe-BN base permanent magnet representative etc. by Nd-Fe-B base permanent magnet representative.Wherein, from having high magnetic and having excellent mass productivity and economical advantage, the R-Fe-B base permanent magnet is particularly preferred.Rare earth based permanent magnet can be the magnet of sintering or bonding magnet.
The rare earth element of rare earth based permanent magnet (R) preferably is selected from least a element among Nd, Pr, Dy, Ho, Tb and the Sm; Or be selected from least a element among La, Ce, Gd, Er, Eu, Tm, Yb, Lu and the Y.
Usually, one of above-mentioned rare earth element is enough to as R, but in the practice, from considerations such as easy acquisitions, can use two or more mixture (mishmetal, didymium etc.).
In addition, be selected from least a element among Al, Ti, V, Cr, Mn, Bi, Nb, Ta, Mo, W, Sb, Ge, Sn, Zr, Ni, Si, Zn, Hf and the Ga by interpolation, can improve the rectangularity and the productivity ratio of coercive force, demagnetization curve, perhaps reduce cost.In addition, by replacing part Fe, can improve the temperature characterisitic of gained magnet, and can not damage magnetic with Co.
Embodiment
By embodiment and comparing embodiment, below the present invention will be described in further detail, but be to be understood that the present invention is not limited thereto.
Embodiment 1
As raw material, mix electrolytic iron, ferroboron and, be mixed into predetermined magnet and form as the Nd of R, and after fusing and casting, products therefrom is crushed and cursorily by the mechanical crushing method fine gtinding, obtains granularity at 3 microns fine powders to 10 micrometer ranges.So the fine powder that obtains is finalized the design under the magnetic field of 10kOe, in argon gas in 1100 ℃ of following sintering 1 hour, and the sintered body of gained was 600 ℃ of following burin-in process 2 hours, obtain consisting of the magnet of 15Nd-7B-78Fe, therefrom cut out the plane sintered magnet coupons of 36 millimeters * 32 millimeters * 3 millimeters sizes, the experiment below accepting.
A. (colourless transparent liquid that comprises 40% weight si acetoacetic ester: wherein silester content changes into SiO by add ethyl silicate 40 in water
2Content), and products therefrom accepts hydrolytic polymerization by regulate its pH value to 3 with the hydrochloric acid of 1N, comprises 20% weight si acetoacetic ester (wherein silester content changes into SiO thereby prepare
2Content) the aqueous solution is as initial raw material.The described aqueous solution of preparation thus mixes with the water-bearing media that has wherein disperseed thin zinc particle, described water-bearing media by in water, add organic dispersing agent (trade mark: SolsperseS20000:Avecia Limited production) and on average major diameter be that the thin zinc particle of sheet of 20 microns (about 20 microns * 20 microns * 1 micron-scales) prepares; After thoroughly stirring products therefrom, use the NaOH of 1N to regulate its pH value to 7.Therefore, obtaining viscosity is 15cP and to comprise total content be that (wherein silester content changes into SiO to 70% weight
2Content) silester is as the aqueous treatment of initial raw material and thin zinc particle, wherein with 9.9: 90: 0.1 (weight ratios; Wherein silester content changes into SiO
2Content) mixing ratio comprises as initial raw-material silester, thin zinc particle and organic dispersing agent.
B. sample supersound washing in ethanol (ungrease treatment), and, immerse in the above-mentioned aqueous treatment after 15 minutes in air dry.The sample that takes out from aqueous treatment is placed in the whizzer, and rotation is 30 seconds under 300rpm, removes the excessive aqueous treatment that adheres on the specimen surface, and predrying 5 minutes of 100 ℃ of following air.In the case, the sample to its predrying aqueous treatment in surface is immersed in the aqueous treatment once more.According to above-mentioned same way as, remove the excessive aqueous treatment that adheres on the specimen surface of from aqueous treatment, taking out, and under 320 ℃ in air, the sample that has the aqueous treatment coated film on its surface is implemented heat treatment 10 minutes, thereby form the anticorrosive film that has wherein disperseed thin zinc particle, wherein the content of thin zinc particle is 90% weight on the specimen surface.Find that the thickness of the anticorrosive film that has wherein disperseed thin zinc particle of formation is about 10 microns (from cross section observations) thus.
C. on 10 samples that have the anticorrosive film that has wherein disperseed thin zinc particle on its surface of so making, implement to be included in 500 hours corrosion resistance test of 35 ℃ of spraying 5% salt solution, and find that the test back does not all have to change (not having iron rust to produce) in appearance to any one sample.
Embodiment 2:
According to embodiment 1 in identical method to prepare the pH value be 3 and comprise 20% weight si acetoacetic ester (wherein silester content changes into SiO
2Content) as the initial raw-material aqueous solution.The aqueous solution of described preparation thus mixes with the water-bearing media that has wherein disperseed thin zinc particle and thin alumina particles, described water-bearing media by in water, add organic dispersing agent (trade mark: SolsperseS20000:Avecia Limited produce), average major diameter is the thin zinc particle of sheet of 20 microns (about 20 microns * 20 microns * 1 micron-scales), and average diameter is that 3 microns thin granular alumina particles prepares; After thoroughly stirring products therefrom, use the NaOH of 1N to regulate its pH value to 7.Therefore, obtaining viscosity is 13cP and to comprise total content be that (wherein silester content changes into SiO to 70% weight
2Content) silester is as the aqueous treatment of initial raw material and thin zinc particle and thin alumina particles, wherein with 9.9: 60: 30: 0.1 (weight ratio; Wherein silester content changes into SiO
2Content) mixing ratio comprises as initial raw-material silester, thin zinc particle, thin alumina particles and organic dispersing agent.According to embodiment 1 in identical method, use the aqueous treatment of gained to form the anticorrosive film that has wherein disperseed thin zinc particle and thin alumina particles on the surface of same sample, the content that wherein thin zinc granule content is 60% weight and thin alumina particles is 30% weight.Find that the thickness that has wherein disperseed the thin zinc particle and the anticorrosive film of thin alumina particles that forms thus is about 10 microns (from cross section observations).According to embodiment 1 in identical method, on 10 samples that have the anticorrosive film that has wherein disperseed thin zinc particle and thin alumina particles on its surface of so making, implement corrosion resistance test, and find that the test back does not all have to change (not having iron rust to produce) in appearance to any one sample.
Embodiment 3:
According to embodiment 1 in identical method, preparation pH value is 3 and comprises 20% weight si acetoacetic ester (wherein silester content changes into SiO
2Content) as the initial raw-material aqueous solution.The aqueous solution of described preparation thus mixes with the water-bearing media that has wherein disperseed thin zinc particle, thin alumina particles and thin tin particles, described water-bearing media by in water, add organic dispersing agent (trade mark: Solsperse S20000:Avecia Limited produce), average major diameter is the thin zinc particle of sheet of 20 microns (about 20 microns * 20 microns * 1 micron-scales), average diameter is 3 microns an acinous alumina particles, and average diameter is that 3 microns thin granulated tin particle prepares; After thoroughly stirring products therefrom, use the NaOH of 1N to regulate its pH value to 7.Therefore, obtaining viscosity is 18cP and to comprise total resultant be that (wherein silester content changes into SiO to 70% weight
2Content) silester is as the aqueous treatment of initial raw material and thin zinc particle, thin alumina particles and thin tin particles, wherein with 9.9: 55: 25: 10: 0.1 (weight ratios; Wherein silester content changes into SiO
2Content) mixing ratio comprises as initial raw-material silester, thin zinc particle, thin alumina particles, thin tin particles and organic dispersing agent.According to embodiment 1 in identical method, on the surface of same sample, use the aqueous treatment of gained to form the anticorrosive film that has wherein disperseed thin zinc particle, thin alumina particles and thin tin particles, the content that wherein thin zinc granule content is 55% weight, thin alumina particles is 25% weight, and the content of thin tin particles is 10% weight.The thickness of finding the anticorrosive film that has wherein disperseed thin zinc particle, thin alumina particles and thin tin particles of formation thus is about 10 microns (from cross section observations).According to embodiment 1 in identical method, on 10 samples that have the anticorrosive film that has wherein disperseed thin zinc particle, thin alumina particles and thin tin particles on its surface of so making, implement corrosion resistance test, and find that the test back does not all have to change (not having iron rust to produce) in appearance to any one sample.
Comparing embodiment 1:
A. prepare the pH value and be 12 and SiO
2/ Na
2O is than the alkaline silicate sodium water solution that is 4.0.The described aqueous solution of preparation thus mixes with the water-bearing media that has wherein disperseed thin zinc particle, described water-bearing media prepares by the thin zinc particle of sheet that to add organic dispersing agent (trade mark: Solsperse S20000:AveciaLimited produce), average major diameter in water be 20 microns (about 20 microns * 20 microns * 1 micron-scales), and thoroughly stirs products therefrom.Therefore, obtaining to comprise total content is that (wherein the alkaline silicate sodium content changes into SiO to 70% weight
2Content) alkaline sodium silicate is as the aqueous treatment of initial raw material and thin zinc particle, wherein with 9.9: 90: 0.1 (weight ratios; Wherein the alkaline sodium silicate ester content changes into SiO
2Content) mixing ratio comprises as initial raw-material alkaline sodium silicate, thin zinc particle and organic dispersing agent.
B. supersound washing in ethanol (ungrease treatment) and air dry 15 minutes with embodiment 1 in identical sample be dipped in the above-mentioned treatment fluid.The sample that takes out from treatment fluid is placed in the whizzer, and rotation is 30 seconds under 300rpm, removes the excessive aqueous treatment that adheres on the specimen surface, and predrying 5 minutes of 100 ℃ of following air.In the case, the sample to its predrying treatment fluid in surface is immersed in the described treatment fluid once more.According to above-mentioned same way as, remove the excessive treatment fluid that adheres on the specimen surface that from aqueous treatment, takes out, and under 150 ℃ in air, the sample that has the treatment fluid coated film on its surface is implemented heat treatment 30 minutes, thereby form the anticorrosive film that has wherein disperseed thin zinc particle, wherein the content of thin zinc particle is 90% weight on the specimen surface.Find that the thickness of the anticorrosive film that has wherein disperseed thin zinc particle of formation is about 10 microns (from cross section observations) thus.
C. on 10 samples that have the anticorrosive film that has wherein disperseed thin zinc particle on last its surface of so making, implement to be included in 500 hours corrosion resistance test of 35 ℃ of spraying 5% salt solution, and find that 7 samples show cosmetic variation (generation iron rust) after 200 hours.
Embodiment 4:
Be 150 microns by average major diameter and consist of the alloy powder that the particle of 12% atom Nd, 77% atom Fe, 6% atom B and 5% atom Co is formed by the preparation of quick curing, and be that the epoxy resin of 2% weight kneads with addition.The gained mixture is at 686N/mm
2The pressure dip mold, then solidified 1 hour down at 150 ℃, obtain external diameter and be 30 millimeters, internal diameter and be 28 millimeters and length and be 4 millimeters ring-type bonded magnet sample.Described sample is accepted the experiment similar with embodiment 1, forms the anticorrosive film that has wherein disperseed thin zinc particle in its surface, and carefully the content of zinc particle is 90% weight.Find that the thickness of the anticorrosive film that has wherein disperseed thin zinc particle of formation is about 10 microns (from cross section observations) thus.In addition, use EPMA (electron probe microanalyzer: the EPM810 type that Shimadzu company produces) observe the cross section of the specimen surface that has formed the anticorrosive film that has wherein disperseed thin zinc particle on its surface.Fig. 7 has provided secondary electron image.Fig. 8 has provided the radioscopic image of zinc.Fig. 9 has provided the radioscopic image of iron.From Fig. 7 to Fig. 9, have been found that zinc is extremely inner from the diffusion into the surface of sample body.Do not observe because the reduction of the magnetic of sample that the diffusion of zinc causes own.On 10 samples that have the anticorrosive film that has wherein disperseed thin zinc particle on its surface of so making, implement to be included in 500 hours corrosion resistance test of 35 ℃ of spraying 5% salt solution, and find that the test back does not all have to change (not having iron rust to produce) in appearance to any one sample.
Embodiment 5:
Regulate the viscosity of the aqueous treatment of preparation among the embodiment 1 to 450cP by adding hydroxyethylcellulose as thickener with the consumption that occupies aqueous treatment 1% weight.Having accepted supersound washing (ungrease treatment) and a large amount of same sample of 15 minutes of air dry in ethanol is placed to and applies as shown in Figure 4 on the anchor clamps, and the coating anchor clamps that are placed with sample above are placed to the roughly form peripheral edge portions of turntable as shown in Figure 6, thereby implement the dipping spin coating by the treatment fluid above using (under 300rpm, implemented centrifugal 30 seconds, remove it).After this, still have the coating anchor clamps of sample above taking off on people's turntable, and still be placed on the sample of coating on the anchor clamps 10 minutes predrying in air under 130 ℃; Implement heat treatment 30 minutes at the sample that in air, on its surface, is formed with the aqueous treatment coated film under 350 ℃ subsequently.Then, the coating anchor clamps that still have sample are above turned over, and be put on the turntable once more, to such an extent as to according to implementing dipping spin coating, predrying and heat treatment with above-mentioned similar methods, thereby form the anticorrosive film that has wherein disperseed thin zinc particle, the content of thin zinc particle is 90% weight on the specimen surface.Find that the thickness of the anticorrosive film that has wherein disperseed thin zinc particle of formation is about 10 microns (from cross section observations) thus.According to mode identical among the embodiment 1, on 10 samples that have the anticorrosive film that has wherein disperseed thin zinc particle on its surface of so making, implement corrosion resistance test, and find that the test back does not all have to change (not having iron rust to produce) in appearance to any one sample.
Embodiment 6:
Regulate the viscosity of the aqueous treatment of preparation among the embodiment 2 to 440cP by adding hydroxyethylcellulose as thickener with the consumption that occupies aqueous treatment 1% weight.By using the aqueous treatment of acquisition like this, in the mode similar to embodiment 5, form the anticorrosive film that has wherein disperseed thin zinc particle and thin alumina particles on the specimen surface identical with embodiment 1 of having accepted supersound washing (ungrease treatment) and air dry 15 minutes, the content that wherein thin zinc granule content is 60% weight and thin alumina particles is 30% weight.Find that the thickness that has wherein disperseed the thin zinc particle and the anticorrosive film of thin alumina particles that forms thus is about 10 microns (from cross section observations).According to embodiment 1 in identical method, on 10 samples that have the anticorrosive film that has wherein disperseed thin zinc particle and thin alumina particles on its surface of so making, implement corrosion resistance test, and find that the test back does not all have to change (not having iron rust to produce) in appearance to any one sample.
Embodiment 7:
Regulate the viscosity of the aqueous treatment of preparation among the embodiment 3 to 460cP by adding hydroxyethylcellulose as thickener with the consumption that occupies aqueous treatment 1% weight.By using the aqueous treatment of acquisition like this, in the mode similar to embodiment 5, on the specimen surface identical of having accepted supersound washing (ungrease treatment) and air dry 15 minutes, form the anticorrosive film that has wherein disperseed thin zinc particle, thin alumina particles and thin tin particles with embodiment 1, the content that wherein thin zinc granule content is 55% weight, thin alumina particles is 25% weight, and the content of thin tin particles is 10% weight.The thickness of finding the anticorrosive film that has wherein disperseed thin zinc particle, thin alumina particles and thin tin particles of formation thus is about 10 microns (from cross section observations).According to embodiment 1 in identical method, on 10 samples that have the anticorrosive film that has wherein disperseed thin zinc particle, thin alumina particles and thin tin particles on its surface of so making, implement corrosion resistance test, and find that the test back does not all have to change (not having iron rust to produce) in appearance to any one sample.
Embodiment 8:
According to embodiment 1 in identical method, preparation pH value is 3 and comprises 20% weight si acetoacetic ester (wherein the alkaline silicate sodium content changes into SiO
2Content) as the initial raw-material aqueous solution.The aqueous solution of described preparation thus mixes with the water-bearing media that has wherein disperseed thin zinc particle, thin alumina particles, thin tin particles and thin alumina particle, described water-bearing media by in water, add organic dispersing agent (trade mark: Solsperse S20000:Avecia Limited produce), average major diameter is the thin zinc particle of sheet of 20 microns (about 20 microns * 20 microns * 1 micron-scales), average diameter is 3 microns acinous alumina particles, the acinous tin particles that average diameter is 3 microns, and average diameter is that 1 micron thin aluminium oxide alumina particles prepares; After thoroughly stirring products therefrom, use the NaOH of 1N to regulate its pH value to 7.Therefore, obtaining viscosity is 16cP and to comprise total content be that (wherein the alkaline silicate sodium content changes into SiO to 70% weight
2Content) silester is as the aqueous treatment of initial raw material and thin zinc particle, thin alumina particles, thin tin particles and thin alumina particle, wherein with 9.9: 55: 25: 8: 2: 0.1 (weight ratios; Wherein the alkaline silicate sodium content changes into SiO
2Content) mixing ratio comprises as initial raw-material silester, thin zinc particle, thin alumina particles, thin tin particles, thin alumina particle and organic dispersing agent.Viscosity by adding the aqueous treatment that hydroxyethylcellulose so prepares as thickener with the consumption that occupies aqueous treatment 1% weight is to 465cP.By using the aqueous treatment of gained, in the mode similar to embodiment 5, on the specimen surface identical of having accepted supersound washing (ungrease treatment) and air dry 15 minutes, form the anticorrosive film that has wherein disperseed thin zinc particle, thin alumina particles, thin tin particles and thin alumina particle with embodiment 1, the content that wherein thin zinc granule content is 55% weight, thin alumina particles is that the content of 25% weight, thin tin particles is 8% weight, and the content of thin alumina particle is 2% weight.The thickness of finding the anticorrosive film that has wherein disperseed thin zinc particle, thin alumina particles, thin tin particles and thin alumina particle of formation thus is about 10 microns (from cross section observations).According to embodiment 1 in identical method, on 10 samples that have the anticorrosive film that has wherein disperseed thin zinc particle, thin alumina particles, thin tin particles and thin alumina particle on its surface of so making, implement corrosion resistance test, and find that the test back does not all have to change (not having iron rust to produce) in appearance to any one sample.
Comparing embodiment 2:
Regulate the viscosity of the treatment fluid of preparation in the comparing embodiment 1 to 420cP by adding hydroxyethylcellulose as thickener with the consumption that occupies treatment fluid 1% weight.By using the treatment fluid of acquisition like this, in predrying condition and heat-treat condition and comparing embodiment 1 are set, use similar, in the mode similar to embodiment 5, form the anticorrosive film that has wherein disperseed thin zinc particle on the specimen surface identical with embodiment 1 of having accepted supersound washing (ungrease treatment) and air dry 15 minutes, wherein thin zinc granule content is 90% weight.Find that the thickness of the anticorrosive film that has wherein disperseed thin zinc particle of formation is about 10 microns (from cross section observations) thus.According to embodiment 1 in identical method, on 10 samples that have the anticorrosive film that has wherein disperseed thin zinc particle on its surface of so making, implement corrosion resistance test, and find that 6 samples show cosmetic variation (generation iron rust) after 200 hours.