CN1279810A - High corrosion-resistant R-Fe-B-base bonded magnet and method of manufacturing the same - Google Patents
High corrosion-resistant R-Fe-B-base bonded magnet and method of manufacturing the same Download PDFInfo
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- CN1279810A CN1279810A CN98811456A CN98811456A CN1279810A CN 1279810 A CN1279810 A CN 1279810A CN 98811456 A CN98811456 A CN 98811456A CN 98811456 A CN98811456 A CN 98811456A CN 1279810 A CN1279810 A CN 1279810A
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- bonded magnet
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- resistant
- high corrosion
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F7/00—Magnets
- H01F7/02—Permanent magnets [PM]
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
Abstract
A method of efficiently manufacturing R-Fe-B-base bonded magnets of various shapes such as ring shape and disk shape having a high corrosion resistance and capable of being plated electrically with ease, wherein the corrosion resistance of the magnet is improved by forming a conductive film of a metal on the surface thereof with tight adhesion, uniformity and efficiency. The method comprises filling the holes of the magnet with polishing powder, inorganic powder and polishing chips, fixing these materials in the holes by fat of a vegetable medium and sealing the resultant holes, and barrel-polishing the magnet by a barrel unit in the dry process with indefinitely shaped, i.e. spherical, massive or acicular (wiry) pieces of a required size of Cu, Sn, Zn, Pb, Cd, In, Au, Ag, Fe, Ni, Co, Cr and Al and such pieces of alloys thereof used as a metallic medium. Said fine pieces of metals such as Cu are press fitted into a resin surface and holes of the bonded magnet and cover the surface and holes and further, cover the surfaces of particles of magnetic powder whereby a very uniform conductive film can be formed on the surface of the bonded magnet, so that it becomes possible to subject the bonded magnet to electric plating excellently and obtain a plated R-Fe-B-base bonded magnet of a high corrosion resistance and with minimum deterioration of the magnetic properties.
Description
Technical field
The present invention relates to make for example bonded permanent magnet of annular or dish type of different shape, its corrosion resistance is improved by the metal film of one deck cleaning, the present invention relates to have the corrosion resistance and close-burning high corrosion-resistant R-Fe-B base bonded magnet and the manufacturing process thereof that are increased sharply.In this technology, at first, fill its hole, with sealing hole and its surface of finishing with polishing powder, bonded permanent magnet buffing and inorganic powder by the dry method bowl-feed technique; Perhaps, do not adopt this encapsulating method, but make metal medium with the alloy block of Cu, Sn, Zn, Pb, Cd, In, Au, Ag, Fe, Ni, Co, Cr, Al and above element, the fine fragment that above-mentioned sheet metal is worn into by the dry method tumbling is pressed into lip-deep hole of bonded permanent magnet and resin surface, forms cover layer; Perhaps,, give magnet surface enough conductivity, make and to carry out Direct Electroplating to it, but not carry out chemical plating by at the fine metal fragment of magnet powder surface coverage one deck; Perhaps, form above-mentioned aluminum cladding earlier, carry out the zinc replacement Treatment then, form a kind of high corrosion-resistant coating of carrying out high efficiency production in enormous quantities, no longer be confined to electronickelling or other reprocessing coating technology.
Background technology
Nowadays, be called as the rubber magnet of bonded permanent magnet and plastic magnet (making different shape) just towards higher serviceability development as annular or dish type, from the isotropic bonded magnet of routine to anisotropic bonded magnet; From the ferrite base bonded magnet to having the more rare earth based bonded permanent magnet of high magnetic intensity, also use the R-Fe-B magnetic material from using the Sm-Co magnetic material to develop into, this R-Fe-B magnetic material has very high magnetic property in sintered magnet, maximum magnetic energy product can reach 50MGOe or higher.
But, there is such problem in the R-Fe-B magnet: because its magnet alloy contains a large amount of iron in forming and very easily the oxidation composition is mutually, so therefore they be easy to get rusty need be with electrolytic deposition, spraying, method forms various compositions on its surface resin bed (visible Japanese Patent Application Publication No.H1-166519/1989, Japanese Patent Application Publication No.H1-245504/1989) such as flood or soak into.
For improving the used resinous coat method of R-Fe-B bonded permanent magnet corrosion resistance, for example, with regard to the used spraying method of ring shape binding magnet, the loss of coating material is big at present; Owing to need the tow sides upset, thereby the processing step that relates to is many; And this method also exists the problem of film thickness uniformity difference.
In addition, for electro-plating method, although thicknesses of layers is even, every block of magnetic all need be linked on the electrode; And plating finishes the trace that rear electrode stays and must remove, and therefore need repair.So this method needs a large amount of processing steps, is particularly suitable for small-sized magnet.
When adopting dipping method,, be difficult to obtain the coating of specific uniform thickness owing to drippage and other problems of coating material.And for the porousness bonded permanent magnet, its hole can not be filled fully, and this can cause the problem that expands in the dry run and so on, and causes the goods adhesion.
For generating metal film coated batch manufacturing method, a kind of scheme is that sintering R-Fe-B magnet is carried out metal plating (visible Japanese Patent Application Publication No.S60-54406/1985 and Japanese Patent Application Publication No.S62-120003/1987), but the surface of R-Fe-B bonded permanent magnet is porousness, and the poorly conductive of its resin that exposes part, therefore, electroplate the back electroplate liquid and can remain in the bonded permanent magnet surface, can not form plated film fully in the resin part, thereby cause pin hole (not plating part); And cause and get rusty.
Therefore, the method that some select electroplate liquid occurring, also is harmless (Japanese Patent Application Publication No.H4-276092/1992) even they infiltrate many cohesives magnet and remain in that.Elder generation also occurred and formed resinous coat, carried out the method (Japanese Patent Application Publication No.H3-11714/1991, Japanese Patent Application Publication No.H4-276095/1992) of plating again at priming coat.
Yet, be difficult to adjust the pH value of plating bath or make them harmless fully, but also do not find any solution that efficient rete forms ability that has, and, the fluctuation of primer thickness is the destabilizing factor of coating, but the priming coat that forms adequate thickness can make and there is no need to carry out overlay coating again.
Someone proposes to adopt this method of plating bath of special component to carry out the nickel plating (Japanese Patent Application Publication No.H4-99192/1992) of high film forming efficiency on the R-Fe-B bonded permanent magnet.But still there is such danger in this method: plating bath can infiltrate bonded permanent magnet, and is wherein residual, causes and gets rusty.
On the other hand, for structural material, the copper strike plating that adopted usually before nickel plating is not a strong basicity, is exactly highly acid, so be not suitable for handling the R-Fe-B bonded permanent magnet yet.
In addition, for making electronic component have resistance to wear, and as the corrosion resistance treatment technology of a kind of fascia and like, practical NiP plating belongs to high-temperature acidic solution class, but this method is not suitable for the R-Fe-B bonded permanent magnet, because it can cause the corrosion of magnet inside.
Therefore,, make plating bath, cleaning solution etc. can not infiltrate and remain in the porousness R-Fe-B bonded permanent magnet, and can efficiently form nickel electrodeposited coating or other coating, and significantly improve its patience, following method is provided for R-Fe-B bonded permanent magnet and manufacture method thereof are provided.
(1) use the mixture plating R-Fe-B base bonded magnet surface of resin and electroconductive powder on substrate material surface, to form the method for conductive film layer.
(2) form on R-Fe-B base bonded magnet surface and have adhering resin bed, the Magnaglo that bonds thereon, and form the method (Japanese Patent Application Publication No.H5-302176/1993) of conductive film layer at substrate material surface.
(3) form conductive film layer with resin and conductive powder on R-Fe-B base bonded magnet surface, carry out the method (Japanese Patent Application Publication No.H9-186016/1997) that surface finish is handled then.
Yet, in above-mentioned three kinds of methods,, therefore can cause process complications inevitably for the hole that seals basis material has used various resin, comprise undesirable resinous coat (soaking into) and sclerosis (finishing processing).
In addition, in method, be difficult to resin is coated in substrate material surface equably with resin-coating (soaking into) basis material, even and use tumbling, the coated product that also is difficult to obtain having excellent accuracy to size subsequently; And, when using conductive coating, include conductive material or metal dust in the resin bed, therefore, even the bonded permanent magnet surface scribbles the basis material that can be better than the R-Fe-B base bonded magnet after the resin part, in manufacture process, still have the part of considerable exposed region and low electric conductivity on the resin cladding surface, thereby the surface that is difficult to obtain to have good homogeneous conductivity, and in electroplating process, easily produce pin hole.
Therefore, the inventor proposes a kind of method: adopt the mixture of the vegetable-derived materials that polishing agent and vegetable-derived materials or surface handled by the inorganic powder modification to do polishing medium, carry out bowl-feed technique with dry method, be bonded at polishing agent powder and bonded permanent magnet buffing in the hole of bonded permanent magnet with the oily components in the vegetable-derived materials, seal its surface of hole and finishing simultaneously, and form conductive layer by electroless copper with alkali plating solution.
Yet this method still has some problems, owing to use electroless copper, the useful life of plating bath is short; And for obtaining good coating layer, the control difficulty of plating bath.In addition, although the corrosion resistance of this method and dimensional accuracy are better than existing technology, nowadays need higher corrosion resistance to adapt to multiple use.
Content of the present invention
One of purpose of the present invention provides the R-Fe-B bonded permanent magnet, and this magnet has high corrosion resistance, even carry out also non-corrosive of high temperature high-temperature test for a long time.Another purpose provides a kind of production method, adopt this method can be formed uniformly various Corrosion Resistant Film on the R-Fe-B bonded permanent magnet, and for to obtain high corrosion resistance, its adhesion strength is also high.
Another object of the present invention provides a kind of manufacture method of high corrosion-resistant R-Fe-B bonded permanent magnet, this method is included in the best industrial production step that magnet surface forms the wear-resistance film layer of high adhesion strength and high size accuracy, and prevents infiltrations such as the plating bath that occurs and cleaning solution and remain in problem in the porousness R-Fe-B bonded permanent magnet in the conventional chemical electroplating method.
The inventor thinks for the R-Fe-B bonded permanent magnet is had in the electro-plating method of excellent corrosion resistance and surface cleanliness, and it is most important to give substrate material surface utmost point uniform conductive, for this reason, the method that obtains above-mentioned conductive film layer has been carried out various researchs.Found that: the R-Fe-B base bonded magnet is carried out the dry method tumbling with drum apparatus, use required size, shape indefinite or spherical, or bulk or needle-like (linear) copper sheet are done metal medium, the fine fragment that grinds of copper can be pressed into the porousness part and the resin surface of bonded permanent magnet, form rete, and the copper fragment also can be coated on the Magnaglo surface, so can form one deck utmost point uniform conductive rete on R-Fe-B bonded permanent magnet surface, therefore good plating can be carried out, thereby excellent corrosion resistance and the magnetic property charged coating R-Fe-B base bonded magnet goods of deterioration hardly can be obtained having.
The inventor has also carried out various researchs, to solve above-mentioned bonded permanent magnet surface smoothness problem.Found that:, use sintering Al by porousness R-Fe-B bonded permanent magnet is carried out the dry method tumbling
2O
3, the polishing agent made of SiC and so on inorganic powder and fruit peel, corn ear and so on the mixture of vegetable-derived materials do polishing medium, perhaps, done polishing medium by the mixture of the vegetable-derived materials after the above-mentioned inorganic powder modification processing with above-mentioned polishing agent and surface, can will constitute the surface oxide layer buffing of the Magnaglo of bonded permanent magnet, modification is bonded at magnet with inorganic powder and polishing agent powder porousness part with the oily components in the vegetable-derived materials, thereby seal its hole, its surface of finishing simultaneously.Therefore, can be directly after the dry method tumbling form the conductivity rete, thereby obtain having the excellent surface fineness and the R-Fe-B base bonded magnet of excellent corrosion resistance more at the magnet substrate material surface.
The inventor recognizes that further except above-mentioned copper sheet, in the dry method tumbling, other material also can be used as metal medium, and promptly Vickers hardness is no more than 80 Sn, Zn, Pb, Cd, In, Au and Ag, and the soft foil metal of Fe, Ni, Co and Cr.
The inventor further finds: by carry out the dry method tumbling in drum apparatus, do metal medium with the aluminium flake that shape is indefinite, the fine fragment that aluminium grinds can be pressed into the porousness part and the resin surface on bonded permanent magnet surface, form rete, perhaps on R-Fe-B bonded permanent magnet surface, carry out the zinc replacement Treatment with the aluminum membranous layer surface that the similar fine fragment of aluminium that is coated in the Magnaglo surface forms, can prevent the aluminium overflow (aluminumeffluence) in the electroplating process like this, guarantee good plating, thereby obtain having excellent corrosion resistance and the magnetic property R-Fe-B base bonded magnet goods of the charged coating of deterioration hardly.Below promptly finished the present invention.Best mode for carrying out the invention
According to the present invention, high corrosion-resistant R-Fe-B base bonded magnet is characterised in that the metal coating that has one deck be formed by the sheet metal of Cu, Sn, Zn, Pb, Cd, In, Au, Ag, Fe, Ni, Co, Cr and Al or its alloy on its surface, above-mentioned sheet metal is pressed into and is coated in porousness part and the resin surface that constitutes R-Fe-B base bonded magnet surface, perhaps this coating forms by being coated in the lip-deep fine metal fragment of the Magnaglo that constitutes described surface, and forms an electrodeposited coating on this intermetallic metal coating.
According to the present invention, the feature of high corrosion-resistant R-Fe-B base bonded magnet is that also its surface has one deck to be pressed into and to be coated in the porousness part that constitutes R-Fe-B base bonded magnet surface and resin surface by above-mentioned metal fragment and the washing layer that forms, perhaps, contained the polishing agent powder in the porousness part that constitutes R-Fe-B base bonded magnet surface, the bonded permanent magnet buffing, and after the filling of the oily components in the vegetable-derived materials of inorganic powder, this coating forms by being coated in the lip-deep fine metal fragment of the Magnaglo that constitutes described surface, and forms an electrodeposited coating on this layer intermetallic metal coating.
According to the present invention, another feature of high corrosion-resistant R-Fe-B base bonded magnet is that it has the layer of aluminum coat, this layer aluminium coating is pressed into and is coated in the porousness part that constitutes described surface and resin surface by fine aluminium chips and form or form by being coated in the lip-deep fine aluminium chips of the Magnaglo that constitutes described surface, this magnet surface has the zinc layer that one deck is formed by the zinc replacement Treatment, forms an electrodeposited coating equally on this intermediate metal layer.
The R-Fe-B base bonded magnet that the present invention considered refers to isotropic bonded magnet and anisotropic bonded magnet, and they can be made by several different methods.For example, in die pressing, elder generation adds thermosetting resin, coupling agent and lubricant and rubs up in the Magnaglo of required composition and performance, carries out mold pressing, heating, resin solidification then; In injection moulding, extrusion molding method or roll extrusion method of molding (rolling molding), elder generation adds thermosetting resin, coupling agent and lubricant and rubs up in Magnaglo, carries out injection moulding, extrusion molding or roll extrusion molding then.
For the R-Fe-B Magnaglo, no matter be isotropism powder or anisotropic powder, all can use, they are made by following any method, comprise: fusing comminuting method (required R-Fe-B alloy melting, casting, then grind), direct reduction-diffusion process (directly obtaining powder) by the Ca reduction, alloy method for quick cooling (required R-Fe-B alloy melting, make the paper tinsel band with the jet casting, then the paper tinsel band is pulverized and annealing), aeroponics (required R-Fe-B alloy melting, make powder and heat treatment with aeroponics), mechanical alloying method (is made powder with required raw material metal, then make fine powder and heat treatment with mechanical alloying method, perhaps HDDR method (required R-Fe-B alloy heats in hydrogen, and it is pulverized and crystallization again).
Among the present invention, 10at%～the 30at% of the total amount of R-Fe-B bonded permanent magnet middle rare earth element R for forming, but preferably contain a kind of in Nd, Pr, Dy, Ho and the Tb element at least, perhaps also contain a kind of in La, Ce, Sm, Gd, Er, Eu, Tm, Yb, Lu and the Y element at least.Common a kind of rare earth element just can meet the demands, but in practice, because the mixture of two or more above rare earth elements is easy to obtain (as mixed rare earth alloy or praseodymium neodymium mixture), also can use these mixtures, R needs not to be a kind of pure rare earth element herein, in addition, considers in industrial feasibility, for example contain unavoidable impurities in the manufacture process, also can use easily.
Rare earth R is indispensable element in above-mentioned magnet powder.Content of rare earth is less than 10at%, and the crystal structure of magnet can become the same cubic crystal of same α-Fe, thereby can not obtain high magnetic property, particularly high coercive force; And on the other hand,, can form the non magnetic phase of many rich R if content of rare earth surpasses 30at%, and make residual magnetic flux density (Br) reduce, can't obtain having the magnet of excellent properties.Therefore, the content of rare earth should be 10at%～30at%.
B also is the essential elements in the above-mentioned magnet powder.If B content is less than 2at%, the water chestnut square structure will become main phase in the magnet, can not obtain high coercive force (iHc) like this; And on the other hand,, can form the non magnetic phase of many rich B if B content is higher than 28at%, and make residual magnetic flux density (Br) reduce, can't obtain excellent magnet.Therefore, B content should be 2at%～28at%.
Fe also is the essential elements in the above-mentioned magnet.Fe content is less than 65at%, and residual magnetic flux density (Br) can reduce; And Fe content surpasses 80at%, can't obtain high coercive force.Therefore, Fe content should be 65at%～80at%.
Replace part Fe with Co, can improve its temperature characterisitic when not damaging the magnet magnetic property, yet the amount that Co substitutes Fe surpasses 20%, magnetic property can descend on the contrary, and this does not wish to take place.When the alternative amount of Co is the 5at%～15at% of Fe, Co total amount, compare with not substituting, Br can raise, so this is suitable for obtaining high magnetic flux density.
In addition, except that R, B and Fe, the impurity that exists inevitably in the industrial production allows, for example, below at least a element substitution part B can improve the productibility of magnet and reduce its cost in the group, this group element is: C (4.0wt% or lower), P (2.0wt% or lower), S (2.0wt% or lower) and Cu (2.0wt% or lower), but its total amount is 2.0wt% or lower.
In Magnaglo, also can add at least a element among Al, Ti, V, Cr, Mn, Bi, Nb, Ta, Mo, W, Sb, Ge, Ga, Sn, Zr, Ni, Si, Zn and the Hf, can improve coercive force, improve the squareness ratio of magnetic hysteresis loop, improve its manufacturability or reduce its cost, the addition upper limit of above element should be in following ranges: this scope can satisfy and obtains bonded permanent magnet (BH)
Max(Br) the required various conditions of desired value.
In addition, in the present invention, the binding agent that injection moulding uses can be as 6PA, 12PA, PPS, the resin of PBT or EVA and so on, in the extrusion molding method, in rolling process (calendar rolling) or the roll extrusion method of molding, binding agent can be PVC, NBR, CPE, NR or Hyperon etc., and spendable binding agent has epoxy resin in mold pressing, DAP or phenolic resins etc., necessary words, can use known metal adhesive, also can use other auxiliary additive, for example assist the lubricant of molding, the coupling agent of binding agent that resin and inorganic filler are used and silylation or titanium base.
Among the present invention, when sealing and finishing processing, the medium that tumbling is used is the mixture of polishing agent and vegetable-derived materials, and this polishing agent for example is Al
2O
3, sintering inorganic powder such as SiC and so on ceramic material or Metal Ball, this vegetable-derived materials for example is plant shell, wood chip, pericarp or maize cob, described polishing with medium or above-mentioned polishing agent and surface by above-mentioned Al
2O
3, the above-mentioned vegetable-derived materials after the inorganic powder modification such as SiC mixture, use said mixture to carry out tumbling as polishing medium, can carry out finishing and encapsulation process to bonded permanent magnet.
For among the present invention for realizing that sealing and finishing are handled and in the dry method tumbling of bonded permanent magnet surface formation metal level, can use known cylinder, as rotating speed commonly used is the rotary roller of 20～50rpm, rotating speed is the centrifugal cylinder of 70～200rpm, perhaps adopt amplitude more than or equal to 0.5mm, but be no more than the oscillatory type cylinder method of 50mm.
In addition, usually the atmosphere during tumbling is air, but for prevent magnet in bowl-feed polishing process because of frictional heat produces oxidation (this is decided by the medium kind), can use N
2, Ar, He gas and so on inert atmosphere, use separately or mix and use.
Among the present invention, when adopting rotary roller or oscillatory type cylinder to seal to handle with finishing, if the bonded permanent magnet in the cylinder of packing into, polishing agent and vegetable-derived materials total amount are less than 20%, processing quantity is not suitable for actual use very little; And surpass 90%, can produce undermixing and can not carry out enough polishings, so its addition should be 20%～90% of an internal capacity.
Among the present invention, the polishing medium that uses during to sealing and finishing processing does not have specific restriction, yet, the particle size of polishing agent should be 1～7mm in the polishing medium mixture, about preferred 3～5mm, and the length of vegetable-derived materials should be 0.5～3mm, about preferred 1～2mm, perhaps described polishing medium is to use above-mentioned polishing agent and above-mentioned its surface by the mixture of vegetable-derived materials after the inorganic powder modification, magnet and polishing medium mixture should stir, and guarantee to produce between them to relatively move.
By the vegetable-derived materials after the inorganic powder modification processing, it is the Al of 0.01～3 μ m that the oily components of the vegetable-derived materials of use such as wax have covered one deck particle size by kneading equably on its surface for above-mentioned surface
2O
3, SiC, ZrO or MgO inorganic powder.The inorganic powder on vegetable-derived materials surface is handled in above-mentioned polishing agent powder as sealant, modification and the buffing granularity of bonded permanent magnet should be 0.01～3 μ m.
In the polishing medium, the ratio (vegetable-derived materials/abrasive material) of vegetable-derived materials and polishing agent must be between 1/5～2, and preferred proportion is 1, and the mixed proportion of bonded permanent magnet and polishing agent (bonded permanent magnet/medium) can be 3 or lower.
Among the present invention, the effect of above-mentioned polishing agent is to grind off effectively the surface oxide layer of magnet, its surface of finishing and bump and sclerosis are by polishing agent powder, the inorganic powder of material surface that is used for improved plant source and the encapsulant that the bonded permanent magnet buffing is formed, thereby the effect of above-mentioned vegetable-derived materials is by emitting the adhesion strength of its oily components enhancing encapsulant effectively.
Among the present invention, surface finish can be reduced to the hole of bonded permanent magnet 3% or lower after handling, and also can not only carry out the finishing encapsulation process to the bonded permanent magnet surface, and the surface oxide layer of removal magnet, thereby obtain active R-Fe-B magnet powder surface.
Among the present invention, can use any known drum apparatus,, can use the sheet metal of indefinite shape, no matter be spherical, piece shape or aciculiform (linear) etc. no matter be rotary, oscillatory type or centrifugal etc. utilize sheet metal to carry out the dry method tumbling.As for the size of sheet metal, if less than 0.1mm, then need the too much time for fully being pressed into and forming coat, be unpractical therefore; And size surpasses 10mm, and its surperficial scrambling strengthens, and uses the impossible all surfaces that covers magnet of this sheet metal, so the size of sheet metal should be 0.1～10mm, and preferred 0.3～5mm, best 0.5～3mm.
In addition, among the present invention, the sheet metal in the dry method of packing into the cylinder needs not to be same shape or size, can be the mixing of multiple shape and size, refining metallic powder is mixed to use also allowing with the indefinite sheet metal of shape.In addition, these sheet metals can be described metal or a kind of alloy or a kind of copper composite metal, and the different metal that its copper heart portion is iron, nickel or aluminium etc. and so on covers.
Also need to make the loading ratio in the dry method tumbling, the volume ratio (magnet/metal) that is magnet and sheet metal is 3 or lower, when this ratio surpasses 3, for making the metal superfine fragment be pressed into magnet and to form the coat required time oversize, be unsuitable for actual use, and magnetic powder particles can produce also on the bonded permanent magnet surface loosening.
Packing into, the quantity of bonded permanent magnet and sheet metal is preferably 20%～90% of polishing machine internal capacity in the tumbling machinery, is lower than 20%, handles quantity very little, is not suitable for actual use; And surpass 90%, and can produce undermixing, can not finish sufficient polishing.
The fine metal fragment that is pressed into and forms coat is powdery or needle-like, and when its length dimension surpasses 5 μ m, this fragment is with the bad adhesion of magnet surface, can cause the bonding defect in the electroplating process and problem such as peel off, therefore, its length should be no more than 5 μ m, preferably is no more than 2 μ m.
Among the present invention, be pressed into and form coat as for the fine metal fragment, the fine metal fragment is barras surface and the porousness part that is pressed into and is coated in the bonded permanent magnet surface, and be coated in the Magnaglo surface on bonded permanent magnet surface, near the surface, the fine metal number of tiles that is pressed into resin surface and porousness part is big, and the quantity that is pressed at the inner place of resin bed reduces gradually.
Among the present invention, metal fragment should be 0.1 μ m or bigger at the layer thickness that is pressed into of resin surface and porousness part, but can not surpass 2 μ m.Be lower than 0.1 μ m, can not obtain enough conductivity, and surpass 2 μ m, although no problem on the performance, the time that needs is long, is not suitable for actual motion.
Washing layer thickness on the Magnaglo surface on bonded permanent magnet surface should be 0.2 μ m or lower, because the reaction between Magnaglo surface and the fine metal fragment belongs to a kind of mechanochemical treatment, if thickness surpasses 0.2 μ m, adhesive property is reduced.
The rotating speed of dry method tumbling should be 20～50rpm for swing roller among the present invention, should be 70～200rpm for centrifugal drum, and is in the vibrator polishing of 0.3～10mm at amplitude, and vibration frequency should be 50～100Hz.
Among the present invention, when use the tumbling method magnet surface form the fine metal fragment be pressed into coat the time, the atmosphere of tumbling can be air.But consider the fine metal fragment that grinds, the Magnaglo of magnet surface, and can cause oxidation as the frictional heat between the sheet metal of the indefinite shape of medium, make conductivity descend, can not electroplate uniformly, thereby cause corrosion proof decline.Therefore, preferred atmosphere is the mixing of inert gas or inactive gas and this class gas in the tumbling method, as N
2, Ar or He.
Among the present invention, the surfaces of aluminum coating will carry out the zinc replacement Treatment to prevent the aluminium overflow in the electroplating process subsequently.The solution that uses in the zinc replacement Treatment contains zinc oxide, NaOH, ferric trichloride or Rossel salt etc.Immerse in the body lotion during processing, bath temperature is 10～25 ℃, and the processing time is 10～120 seconds.
In the zinc replacement process, process sequence should be cleaning → zinc displacement → cleaning.If the aluminum cladding surface exists pollutant or other sticky materials, cleaning process should be soaked oil removing in sodium carbonate and sodium tripolyphosphate solution.When forming the zinc displacement layer, its superficial layer should be ZnO
x(x=0～1) form, the thickness that forms the zinc layer is 0.1 μ m or lower.If the thickness of this layer zinc layer surpasses 0.1 μ m, can cause bonding defect, so should avoid like this.
Among the present invention, electro-plating method should contain at least a metal that is selected from the alloy that Ni, Cu, Sn, Co, Zn, Cr, Ag, Au, Pb and Pt or its contain B, S or P, electronickelling especially can meet the demands, and electrodeposited coating thickness should be 50 μ m or lower, preferred 10～30 μ m.Can use watt groove commonly used to electroplate among the present invention, be pressed into coat to effectively utilize the above-mentioned fine metal fragment that in resin surface and porousness part, forms, thereby obtain excellent bond performance and corrosion resistance.
Specifically, in the electro-plating method that uses nickel plating bath to carry out, sequence of process steps should be cleaning → electronickelling → cleaning → oven dry, and the pH value of nickel-plating liquid should use alkaline carbonic acid nickel to be adjusted to 4.0～4.6, and treatment temperature should be 50～60 ℃.
In electronickelling, should use above-mentioned electroplate liquid to introduce predetermined electric current, make anode with sheet nickel, the nickel of Nickel Anode Plate is stably deposited, can use the Estland nickel sheet of sulfur-bearing in electrode, in using the electro-plating method of nickel plating solution, process sequence should be cleaning → plating → cleaning → oven dry, wherein, oven dry is preferably carried out under 70 ℃ or higher temperature.
Can use various electroplating bath, this is decided by the shape of bonded permanent magnet, for ring shape binding magnet, preferably uses nose suspension type (rack plating) electro-plating method or cylinder electro-plating method.
Embodiment
Embodiment 1
The alloy powder particle mean size of using is 150 μ m, and composition is 12at%Nd, 77at%Fe, 6at%B and 5at%Co, makes with superelevation cooling rate method, adds the epoxy resin of 2wt%, rub up together, and at 7 tons/cm
2Pressure use down press forming, follow 170 ℃ of temperature-curable 1 hour, producing ring shape binding magnet, its external diameter 22mm, internal diameter 20mm, high 3mm, the bonded permanent magnet performance that obtains like this is as follows: Br=6.7kG, iHc=8.9kOe, (BH)
Max=9.0MGOe.
Use the stub shape copper rod of diameter as 1mm, long 1mm, above-mentioned bonded permanent magnet is put into the oscillatory type cylinder carry out the dry method tumbling, to form the conductive layer that constitutes by fine copper fragment on the bonded permanent magnet surface, the overlay film layer thickness that is pressed into of copper fragment is about 0.7 μ m on the resin surface, and the thicknesses of layers on Magnaglo surface is 0.1 μ m.
The condition that tumbling is handled is as follows: atmosphere is argon gas, packing into, (apparent volume is 0.15 liter to 50 bonded permanent magnets, heavy 100g) and the copper fragment of above-mentioned size (apparent volume is 2 liters, heavy 10kg), the vibrator volume is 3.5 liters, vibration frequency 70Hz, amplitude 3mm, the cumulative volume charge weight is 60% of an internal roll, and the processing time is 3 hours.
Then clean, and carry out electronickelling with the nose suspension type electroplanting device, electroplate back inner radius coating film thickness 20 μ m, outer radius is 22 μ m.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.After the moisture resistivity test, the performance of magnet sees Table 1, and surface state and thicknesses of layers accuracy to size during the moisture resistivity test see Table 2.
The electronickelling condition is as follows: current density 2A/dm
2, electroplating time 60 minutes, electroplate liquid pH value is 4.2, temperature is 55 ℃.Electroplating bath components is: 240g/l nickelous sulfate, 45g/l nickel chloride, titration nickelous carbonate (in order to adjust the pH value) and 30g/l boric acid.
Comparative Examples 1
Clean the ring shape binding magnet of using method similarly to Example 1 to obtain, afterwards it is carried out electroless copper, thickness of coating 5 μ m, electronickelling under the condition identical then with embodiment 1, ring shape binding magnet after handling is like this carried out environmental test, 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.The results are shown in Table 1～3.
The electroless copper condition is as follows: 20 minutes plating time, bath pH value is 11.5, and bath temperature is 20 ℃.Solution composition is: 29g/l copper sulphate, 25g/l sodium carbonate, 140g/l tartrate, 40g/l NaOH and 150ml concentration are 37% formaldehyde.Comparative Examples 2
Clean the ring shape binding magnet of using method similarly to Example 1 to obtain, form the thick conducting film of 10 μ m with the phenolic resins that is mixed with nickel powder afterwards, electronickelling under the condition identical then with embodiment 1, ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.The results are shown in Table 1～3.
The formation condition of conductive film layer is as follows: in 30 minutes processing times, the Treatment Solution composition is: the phenolic resins of 5wt%, the MEK (butanone) of the nickel powder of 5wt% (granularity 0.7 μ m or lower) and 90wt%.Comparative Examples 3
Clean the ring shape binding magnet of using method similarly to Example 1 to obtain, on magnet, form one deck tack coat by dipping method in advance with phenolic resins afterwards, then at its surface adhesion silver powder (granularity 0.7 μ m or lower), form the thick conductive film layer of 7 μ m with the oscillatory type cylinder afterwards, vibrator is handled back electronickelling under the condition identical with embodiment 1, ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.The results are shown in Table 1～3.
The condition of oscillatory type roller process is as follows: the vibrator volume is 3.5 liters, 50 bonded permanent magnets of packing into, and in 3 hours processing times, the employing diameter is that 2.5mm, apparent volume are that 2 liters steel ball is as medium.
Can obviously find out from table 1 and table 2: Comparative Examples 1 after 100 hours, Comparative Examples 2 after 300 hours, Comparative Examples 3 the spot corrosion all occurred after about 350 hours; And opposite, for embodiment 1, even through 500 hours, the spot corrosion does not appear under 30 power microscopes yet.Table 1
Magnetic property reduces ratio (%)=[{ (initial magnetic property)-(moisture resistivity test back magnetic property) }/(initial magnetic property)] * 100 tables 2
Embodiment 2
| Before the moisture resistivity test | After the moisture resistivity test | Magnetic property reduces ratio (%) | |||||||
| Br (kG) | iHc (kOe) | (BH) max(MGOe) | Br (kG) | iHc (kOe) | (BH) max(MGOe) | Br (kG) | iHc | (BH) max(MGOe) | |
| Embodiment 1 | ?6．6 | ?8．9 | ?9．0 | ?6．5 | ?8．7 | ?8．8 | ?3．0 | ?2．2 | ?2．2 |
| Comparative Examples 1 | ?6．4 | ?8．7 | ?8．8 | ?5．7 | ?7．7 | ?7．6 | ?14．9 | ?15．6 | ?15．5 |
| Comparative Examples 2 | ?6．4 | ?8．9 | ?9．0 | ?6．3 | ?8．5 | ?8．5 | ?6．3 | ?4．4 | ?5．5 |
| Comparative Examples 3 | ?6．4 | ?8．9 | ?9．0 | ?6．3 | ?8．5 | ?8．5 | ?6．3 | ?4．4 | ?5．5 |
| Surface state after certain moisture resistivity test duration | Thicknesses of layers accuracy to size (μ m) | Manufacture method | |
| Embodiment 1 | No change (non-corroding) | 20±1 | Cu rete+Ni coating |
| Comparative Examples 1 | Appearance point corrosion behind the 100h | 25±2 | Electroless Cu Plating coating+Ni coating |
| Comparative Examples 2 | The tiny dots corrosion appears behind the 300h | 30±10 | Resin conductive layer+Ni coating |
| Comparative Examples 3 | The tiny dots corrosion appears behind the 350h | 27±10 | Conductive coating+Ni coating |
The alloy powder particle mean size of using is 150 μ m, and composition is 12at%Nd, 77at%Fe, 6at%B and 5at%Co, makes with superelevation cooling rate method, adds the epoxy resin of 2wt%, rub up together, and at 7 tons/cm
2Pressure use down press forming, follow 170 ℃ of temperature-curable 1 hour, producing ring shape binding magnet, its external diameter 26mm, internal diameter 24mm, high 5mm, the bonded permanent magnet performance that obtains like this is as follows: Br=6.8kG, iHc=9.1kOe, (BH)
Max=9.2MGOe.
With 100 such magnets (200g) is the Al of 3mm with average diameter
2O
3It is 20 liters oscillatory type cylinder that base ball-shape drum abrasive material is put into volume, and packing into accounts for the vegetable-derived materials of cylinder volume 50%, and vegetable-derived materials be surperficial by the Al of the about 1 μ m of granularity
2O
3The juglandis,semen of that powder modification was handled, the about 1mm of diameter carries out 120 minutes dry method surface finish then, and amplitude is 20mm, handles with sealing magnet space and finishing.
Then, bonded permanent magnet packed into carry out the dry method tumbling in the oscillatory type cylinder, vibration frequency 70Hz, amplitude 3mm, atmosphere is argon gas, the stub shape copper rod that with diameter is 1mm, long 1mm forms the conductive layer that is made of fine copper fragment on the bonded permanent magnet surface, and the degree of depth that fine copper fragment is pressed into resin surface and porousness part is about 0.7 μ m, and the thicknesses of layers on Magnaglo surface is 0.1 μ m.The condition that tumbling is handled is as follows: (apparent volume is 0.15 liter to 50 bonded permanent magnets of packing into, heavy 100g) and the copper fragment of above-mentioned size (apparent volume is 2 liters, heavy 10kg), the vibrator volume is 3.5 liters, processing time is 3 hours, amplitude 20mm, cumulative volume charge weight are 60% of internal roll.
Then clean, and carry out electronickelling with the nose suspension type electroplanting device, electroplate back inner radius coating film thickness 21 μ m, outer radius is 23 μ m.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 800 hours.After the moisture resistivity test, the performance of magnet sees Table 3, and surface state and thicknesses of layers accuracy to size after certain moisture resistivity test duration see Table 4.
The electronickelling condition is as follows: current density 2A/dm
2, electroplating time 60 minutes, electroplate liquid pH value is 4.2, temperature is 55 ℃.Electroplating bath components is: 240g/l nickelous sulfate, 45g/l nickel chloride, titration nickelous carbonate (in order to adjust the pH value) and 30g/l boric acid.Comparative Examples 4
Clean the ring shape binding magnet of using method similarly to Example 2 to obtain, sealing and the surface finish carried out are afterwards similarly to Example 2 handled, and clean once more, then it are carried out electroless copper, thickness of coating 5 μ m.Electronickelling under the condition identical behind the electroless copper with embodiment 2, ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test) under the condition identical with embodiment 2, experiment with measuring result and thicknesses of layers accuracy to size (moisture resistivity test) the results are shown in Table 3 and table 4.
The electroless copper condition is as follows: 20 minutes plating time, plating bath state value is 11.5, and temperature is 20 ℃.Solution composition is: 29g/l copper sulphate, 25g/1 sodium carbonate, 140g/1 tartrate, 40g/l NaOH and 150ml concentration are 37% formaldehyde.Comparative Examples 5
Clean the ring shape binding magnet of using method similarly to Example 2 to obtain, mixture with phenolic resins and nickel powder forms the thick electroconductive resin film of 10 μ m in magnet surface under the following conditions afterwards, the magnet and the 5mm copper ball of packing in the oscillatory type cylinder then and accounting for its volume 60% are that the tumbling of carrying out under the 20mm condition 60 minutes is also polished with finishing at amplitude.
Electronickelling under the condition identical then with embodiment 2, ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test) under the condition identical with embodiment 2, experiment with measuring result and thicknesses of layers accuracy to size (moisture resistivity test) the results are shown in Table 3 and table 4.
The formation condition of conduction coat is as follows: in 30 minutes processing times, the Treatment Solution composition is: the phenolic resins of 5wt%, the MEK (butanone) of the nickel powder of 5wt% (granularity 0.7 μ m or lower) and 90wt%.
Can find out from table 4: Comparative Examples 4 after 700 hours, the spot corrosion all appearred in Comparative Examples 5 after 600 hours: and on the other hand, for embodiment 2, even through 800 hours, the spot corrosion does not appear under 30 power microscopes yet.Table 3
Magnetic property reduces ratio (%)=[{ f (initial magnetic property)-(moisture resistivity test back magnetic property) }/(initial magnetic property)] * 100 tables 4
Embodiment 3
| Before the moisture resistivity test | After the moisture resistivity test | Magnetic property reduces ratio (%) | |||||||
| Br (kG) | iHc (kOe) | (BH) max(MG0e) | Br (kG) | iHc (kOe) | (BH) max(MGOe) | Br (kG) | iHc (kOe) | (BH) max(MGOe) | |
| Embodiment 2 | ?6．7 | ?9．0 | ?9．1 | ?6．5 | ?8．7 | ?8．7 | ?4．4 | ?4．4 | ?5．4 |
| Comparative Examples 4 | ?6．7 | ?8．9 | ?9．1 | ?6．3 | ?8．5 | ?8．3 | ?7．4 | ?6．6 | ?9．8 |
| Comparative Examples 5 | ?6．7 | ?9．0 | ?9．1 | ?6．3 | ?8．7 | ?8．2 | ?7．4 | ?7．7 | ?10．9 |
| Surface state after certain moisture resistivity test duration | Thicknesses of layers accuracy to size (μ m) | Manufacture method | |
| Embodiment 2 | No change (non-corroding) | 22±1 | Encapsulation process+Cu rete+Ni coating |
| Comparative Examples 4 | Appearance point corrosion behind the 700h | 25±2 | Encapsulation process+Electroless Cu Plating+Ni coating |
| Comparative Examples 5 | Appearance point corrosion behind the 600h | 28±5 | Resin conductive layer+finishing Ni coating |
Make the ring shape binding magnet of 25mm (external diameter) * 23mm (internal diameter) * 3mm (height) with the method identical with embodiment 1, its performance is as follows: Br=6.9kG, and iHc=9.1kOe, (BH)
Max=9.3MGOe.
Above-mentioned bonded permanent magnet is put into the oscillatory type cylinder carry out the dry method tumbling, use diameter to form the conductive layer that constitutes by fine tin fragment on the bonded permanent magnet surface as the stub shape tin bar of 2mm, long 1mm, the thickness that is pressed into of tin fragment is about 0.9 μ m on the resin surface, and the coating layer thickness on Magnaglo surface is 0.4 μ m.Condition when tumbling is handled is with embodiment 1.
Then clean, and carry out electro-coppering with the nose suspension type electroplanting device, carry out electronickelling then, electroplate back inner radius coating film thickness 22 μ m, outer radius is 23 μ m.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.After the moisture resistivity test, the performance of magnet sees Table 5, and surface state and thicknesses of layers accuracy to size after certain moisture resistivity test duration see Table 6.
The electro-coppering condition is as follows: current density 2.5A/dm
2, electroplating time 5 hours, electroplate liquid pH value is 10, temperature is 40 ℃.Electroplating bath components is: 20g/l copper, the 10g/l cyanogen that dissociates.The electronickelling condition is with embodiment 1.
Embodiment 4
To put into the oscillatory type cylinder with the ring shape binding magnet that method is similarly to Example 3 made and carry out the dry method tumbling, use diameter to form the conductive layer that constitutes by fine zinc fragment on the bonded permanent magnet surface as the stub shape zinc bar of 1mm, long 2mm, the thickness that is pressed into of zinc fragment is about 0.8 μ m on the resin surface, and the coating layer thickness on Magnaglo surface is 0.2 μ m.Condition when tumbling is handled is with embodiment 1.
Then under condition similarly to Example 3, electroplate copper and mickel, the ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.After the moisture resistivity test, the performance of magnet sees Table 5, and surface state and thicknesses of layers accuracy to size after the moisture resistivity test see Table 6.
Embodiment 5
To put into the oscillatory type cylinder with the ring shape binding magnet that method is similarly to Example 3 made and carry out the dry method tumbling, use diameter to form the conductive layer that constitutes by fine plumbous fragment on the bonded permanent magnet surface as the stub shape lead rod of 1mm, long 1mm, the thickness that is pressed into of plumbous fragment is about 0.9 μ m on the resin surface, and the coating layer thickness on Magnaglo surface is 0.6 μ m.Condition when tumbling is handled is with embodiment 1.
Then under condition similarly to Example 3, electroplate copper and mickel, the ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.After the moisture resistivity test, the performance of magnet sees Table 5, and surface state and thicknesses of layers accuracy to size after the moisture resistivity test see Table 6.Comparative Examples 6
Clean the ring shape binding magnet made from embodiment 3 same methods, it is carried out electroless copper, the thick 5 μ m of coating.Behind the electroless copper, under condition similarly to Example 3, electroplate copper and mickel, the ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.After the moisture resistivity test, the performance of magnet sees Table 5, and surface state and thicknesses of layers accuracy to size after the moisture resistivity test see Table 6.The chemical-copper-plating process condition is with Comparative Examples 1.Comparative Examples 7
Clean the ring shape binding magnet made from embodiment 3 same methods, mixture with phenolic resins and nickel powder forms the thick conductive film layer of 10 μ m on its surface, under condition similarly to Example 3, electroplate copper and mickel then, ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.After the moisture resistivity test, the performance of magnet sees Table 5, and surface state and thicknesses of layers accuracy to size after the moisture resistivity test see Table 6.The chemical-copper-plating process condition is with Comparative Examples 2.Comparative Examples 8
Clean the ring shape binding magnet made from embodiment 3 same methods, form the phenolic resin bonded layer of one deck on its surface by dipping method, then at its surface adhesion silver powder (granularity 0.7 μ m or lower), form the thick conductive film layer of 7 μ m with the oscillatory type cylinder afterwards, under condition similarly to Example 3, electroplate copper and mickel then.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.After the moisture resistivity test, the performance of magnet sees Table 5, and surface state and thicknesses of layers accuracy to size after the moisture resistivity test see Table 6.The chemical-copper-plating process condition is with Comparative Examples 3.Table 5
Magnetic property reduces ratio (%)=[{ (initial magnetic property)-(moisture resistivity test back magnetic property) }/(initial magnetic property)] * 100 tables 6
From table 5～6 as seen: Comparative Examples 6 after about 130 hours, Comparative Examples 7 after 250 hours, Comparative Examples 8 origination point corrosion after 330 hours; On the contrary, embodiment 3 does not observe a corrosion yet under 30 power microscopes after 500 hours.
| Before the moisture resistivity test | After the moisture resistivity test | Magnetic property reduces ratio (%) | |||||||
| ?Br (kG) | ihc (kOe) | (BH)max (MGOe) | ?Br (kG) | iHc (kOe) | (BH)max (MGOe) | ?Br (kG) | iHc (kOe) | (BH)max (MGOe) | |
| Embodiment 3 | ?6.7 | ?9.0 | ?9.0 | ?6.7 | ?8.9 | ?9.0 | ?2.8 | ?2.2 | ?3.2 |
| Embodiment 4 | ?6.7 | ?9.0 | ?9.0 | ?6.7 | ?8.8 | ?9.0 | ?2.8 | ?3.2 | ?3.2 |
| Embodiment 5 | ?6.7 | ?9.0 | ?9.0 | ?6.6 | ?8.8 | ?8.9 | ?4.4 | ?3.3 | ?4.3 |
| Comparative Examples 6 | ?6.5 | ?8.7 | ?8.8 | ?5.8 | ?7.6 | ?7.7 | ?15.9 | ?16.5 | ?17.2 |
| Comparative Examples 7 | ?6.5 | ?8.9 | ?8.9 | ?6.2 | ?8.4 | ?8.5 | ?10.1 | ?7.7 | ?8.6 |
| Comparative Examples 8 | ?6.5 | ?8.9 | ?9.0 | ?6.2 | ?8.5 | ?8.5 | ?10.1 | ?6.6 | ?8.6 |
| Surface state after certain moisture resistivity test duration | Thicknesses of layers accuracy to size (μ m) | Manufacture method | |
| Embodiment 3 | No change (non-corroding) | 22±1 | Sn coat+Cu, Ni coating |
| Embodiment 4 | No change (non-corroding) | 22±1 | Zn coat+Cu, Ni coating |
| Embodiment 5 | No change (non-corroding) | 22±1 | Pb coat+Cu, Ni coating |
| Comparative Examples 6 | Appearance point corrosion behind the 130h | 26±2 | Chemical plating copper layer+Cu, Ni coating |
| Comparative Examples 7 | A small amount of corrosion appears behind the 250h | 32±9 | Resin conductive layer+Cu, Ni coating |
| Comparative Examples 8 | A small amount of corrosion appears behind the 330h | 28±10 | Conductive film layer+Cu, Ni coating |
Embodiment 6
Make the ring shape binding magnet of 34mm (external diameter) * 31mm (internal diameter) * 8mm (height) with the method identical with embodiment 1, its performance is as follows: Br=6.7kG, and iHc=9.1kOe, (BH)
Max=9.1MGOe.
It is the Al of 3mm that above-mentioned bonded permanent magnet is put into oscillatory type cylinder average diameter
2O
3The ball-shape drum abrasive material seals with finishing and handles.Its process conditions and using method are with embodiment 2.
Then above-mentioned bonded permanent magnet is put into the oscillatory type cylinder carries out the dry method tumbling, use diameter to form the conductive layer that constitutes by the fine metal fragment on the bonded permanent magnet surface, see Table 7 with the fine metal fragment compression distance of porousness part and the coat thickness on Magnaglo surface on the resin surface as stub shape tin, zinc and the lead rod of 1mm, long 1mm.Condition when tumbling is handled is with embodiment 2.
Then clean, and carry out electro-coppering with the nose suspension type electroplanting device, carry out electronickelling then, electroplate back inner radius coating film thickness 21 μ m, outer radius is 22 μ m.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 1000 hours.Its result of the test and thicknesses of layers accuracy to size see Table 8 and table 9.Process conditions when electroplating copper and mickel are with embodiment 2.Comparative Examples 9
Clean the ring shape binding magnet of using method similarly to Example 6 to obtain, sealing and the surface finish carried out are afterwards similarly to Example 6 handled, and clean once more, then it are carried out electroless copper, thickness of coating 5 μ m.Under the condition identical, carry out copper facing and nickel plating behind the electroless copper with embodiment 6.
Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test) under the condition identical with embodiment 6, before the moisture resistivity test and the magnetic property after the test see Table 8, surface appearance and thicknesses of layers accuracy to size after moisture resistivity is tested see Table 9.The process conditions of electroless copper are with Comparative Examples 4.Comparative Examples 10
Clean the ring shape binding magnet of using method similarly to Example 6 to obtain, mixture with phenolic resins and nickel powder forms the thick electroconductive resin coat of 10 μ m in magnet surface afterwards, the magnet and the 5mm steel ball of packing in the oscillatory type cylinder then and accounting for its volume 60% are that the tumbling of carrying out under the 20mm condition 60 minutes is also polished with finishing at amplitude.
Electro-coppering and electronickelling under the condition identical with embodiment 6 then carried out environmental test (moisture resistivity test) with the ring shape binding magnet after handling like this under the condition identical with embodiment 6, its result of the test and thicknesses of layers accuracy to size see Table 8 and table 9.Conduction coat treatment conditions are with Comparative Examples 5.Table 7
Table 8
Magnetic property reduces ratio (%)=[{ (initial magnetic property)-(moisture resistivity test back magnetic property) }/(initial magnetic property)] * 100 tables 9
| Metal fragment | The compression distance that resin surface and porousness are partly located (μ m) | The coating thickness on Magnaglo surface (μ m) |
| ????Sn | ????0．9 | ????0．4 |
| ????Zn | ????0．7 | ????0．3 |
| ????Pb | ????0．9 | ????0．5 |
| Before the moisture resistivity test | After the moisture resistivity test | Magnetic property reduces ratio (%) | |||||||
| Br (kG) | iHc (kOe) | (BH) max(MGOe) | Br (kG) | iHc (kOe) | (BH) max(MGOe) | Br (kG) | iHc (kOe) | (BH) max(MGOe) | |
| Embodiment 6 Sn | ?6．6 | ?9．0 | ?9．0 | ?6．4 | ?8．6 | ?8．6 | ?4．5 | ?5．5 | ?5．5 |
| Embodiment 6 Zn | ?6．6 | ?9．0 | ?9．0 | ?6．3 | ?8．6 | ?8．6 | ?6．0 | ?5．5 | ?5．5 |
| Embodiment 6 Pb | ?6．6 | ?9．0 | ?9．0 | ?6．3 | ?8．5 | ?8．5 | ?6．0 | ?6．6 | ?6．6 |
| Comparative Examples 9 | ?6．6 | ?8．9 | ?9．0 | ?6．2 | ?8．4 | ?8．3 | ?7．5 | ?7．7 | ?8．8 |
| Comparative Examples 10 | ?6．6 | ?9．0 | ?9．0 | ?6．0 | ?8．2 | ?8．1 | ?10．4 | ?9．9 | ?11．0 |
| Surface state after the moisture resistivity test | Thicknesses of layers accuracy to size (μ m) | Manufacture method | |
| Embodiment 6 Sn | No change (non-corroding) | 22±1 | Encapsulation process+Sn rete+Cu, Ni coating |
| Embodiment 6 Zn | No change (non-corroding) | 22±1 | Encapsulation process+Zn rete+Cu, Ni coating |
| Embodiment 6 Pb | No change (non-corroding) | 22±1 | Encapsulation process+Pb rete+Cu, Ni coating |
| Comparative Examples 9 | Appearance point corrosion behind the 800h | 27±2 | Encapsulation process+electroless copper+Cu, Ni coating |
| Comparative Examples 10 | Appearance point corrosion behind the 600h | 30±5 | Resin conductive layer+finishing and polishing+Cu, Ni coating |
Can find out from table 9: Comparative Examples 9 after about 800 hours, Comparative Examples 10 all appearance point corrosions after 600 hours; And on the other hand,,, under 30 power microscopes, do not have the appearance point corrosion even through 1000 hours for embodiment 6 yet.
Embodiment 7
Make the ring shape binding magnet of 21mm (external diameter) * 18mm (internal diameter) * 4mm (height) with the method identical with embodiment 1, its performance is listed in table 11:Br=6.8kG, iHc=9.1kOe, (BH)
Max=9.2MGOe.
Above-mentioned bonded permanent magnet is put into the oscillatory type cylinder carry out the dry method tumbling, use diameter to form the conductive cladding that is made of these fine metal fragments as stub shape Fe, Ni, Co and the Cr rod of 0.7mm, long 0.5mm on the bonded permanent magnet surface, the fine metal fragment compression distance on the resin surface and the coat thickness on Magnaglo surface see Table 10.Condition when tumbling is handled is with embodiment 1.
Then clean, and carry out electro-coppering with the nose suspension type electroplanting device, carry out electronickelling then, electroplate back inner radius coating film thickness 18 μ m, outer radius is 21 μ m.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.The performance of moisture resistivity test back magnet sees Table 12, and surface appearance and thicknesses of layers accuracy to size after the moisture resistivity test see Table 13.Process conditions when electro-coppering and electronickelling are with embodiment 1.Comparative Examples 11
Clean the ring shape binding magnet of using method similarly to Example 7 to obtain, then it is carried out electroless copper, thickness of coating 6 μ m.Under condition similarly to Example 3, electroplate copper and mickel behind the electroless copper.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.The magnetic property of moisture resistivity test back magnet sees Table 12, and surface appearance and thicknesses of layers accuracy to size after the moisture resistivity test see Table 13.The process conditions of electroless copper are with Comparative Examples 1.Comparative Examples 12
Clean the ring shape binding magnet that obtains with similarly to Example 7 method, the mixture with phenolic resins and nickel powder forms the thick conduction coat of 10 μ m in magnet surface afterwards, after this processing end, electroplates copper and mickel under the process conditions identical with embodiment 7.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.The magnetic property of moisture resistivity test back magnet sees Table 12, and surface appearance and thicknesses of layers accuracy to size after the moisture resistivity test see Table 13.The formation condition of resin conduction coat is with Comparative Examples 2.Comparative Examples 13
Clean the ring shape binding magnet of using method similarly to Example 7 to obtain, form the phenolic resin bonded layer of one deck on its surface by dipping method, then at its surface adhesion silver powder (granularity 0.7 μ m or lower), in the oscillatory type cylinder, form the thick conductive film layer of 7 μ m afterwards, under condition similarly to Example 7, electroplate copper and mickel then.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.After the moisture resistivity test, the performance of magnet sees Table 12, and surface state and thicknesses of layers accuracy to size during the moisture resistivity test see Table 13.The chemical-copper-plating process condition is with Comparative Examples 3.Table 10
Table 11
Table 12
Magnetic property reduces ratio (%)=[{ (initial magnetic property)-(moisture resistivity test back magnetic property) }/(initial magnetic property)] * 100 tables 13
| Metal fragment | The compression distance that resin surface and porousness are partly located (μ m) | The coating thickness on Magnaglo surface (μ m) |
| ??Fe | ????0．5 | ????0．1 |
| ??Ni | ????0．4 | ????0．1 |
| ??Co | ????0．3 | ????0．1 |
| ??Cr | ????0．3 | ????0．1 |
| The parent material magnetic property | |||
| ????Br(kG) | ????iHc(kOe) | ????(BH) max(MGOe) | |
| Embodiment 7 Fe | ????6．8 | ????9．1 | ????9．2 |
| Embodiment 7 Ni | ????6．8 | ????9．1 | ????9．2 |
| Embodiment 7 Co | ????6．8 | ????9．1 | ????9．2 |
| Embodiment 7 Cr | ????6．8 | ????9．1 | ????9．2 |
| Comparative Examples 11 | ????6．8 | ????9．1 | ????9．2 |
| Comparative Examples 12 | ????6．8 | ????9．1 | ????9．2 |
| Comparative Examples 13 | ????6．8 | ????9．1 | ????9．2 |
| Before the moisture resistivity test | After the moisture resistivity test | Magnetic property reduces ratio (%) | |||||||
| Br (kG) | iHc (kOe) | (BH) max(MGOe) | Br (kG) | iHc (kOe) | (BH) max(MGOe) | Br (kG) | iHc | (BH) max(MGOe) | |
| Embodiment 7 Fe | ?6．7 | ?9．0 | ?9．0 | ?6．4 | ?8．7 | ?8．7 | ?5．9 | ?4．4 | ?5．5 |
| Embodiment 7 Ni | ?6．7 | ?9．0 | ?9．0 | ?6．4 | ?8．7 | ?8．7 | ?5．9 | ?4．4 | ?5．5 |
| Embodiment 7 Co | ?6．7 | ?9．0 | ?9．0 | ?6．4 | ?8．6 | ?8．7 | ?5．9 | ?5．5 | ?5．5 |
| Embodiment 7 Cr | ?6．7 | ?9．0 | ?9．0 | ?6．4 | ?8．6 | ?8．6 | ?5．9 | ?5．5 | ?6．6 |
| Comparative Examples 11 | ?6．4 | ?8．7 | ?8．7 | ?5．7 | ?7．7 | ?7．7 | ?16．2 | ?15．4 | ?16．3 |
| Comparative Examples 12 | ?6．6 | ?8．9 | ?9．0 | ?6．3 | ?8．5 | ?8．5 | ?7．4 | ?6．6 | ?7．6 |
| Comparative Examples 13 | ?6．6 | ?9．0 | ?9．0 | ?6．3 | ?8．4 | ?8．5 | ?7．4 | ?7．7 | ?7．6 |
| Surface state after the moisture resistivity test | Thicknesses of layers accuracy to size (μ m) | Manufacture method | |
| Embodiment 7 Fe | No change (non-corroding) | 18±2 | Fe coat+Ni coating |
| Embodiment 7 Ni | No change (non-corroding) | 18±2 | Ni coat+Ni coating |
| Embodiment 7 Co | No change (non-corroding) | 18±2 | Co coat+Ni coating |
| Embodiment 7 Cr | No change (non-corroding) | 18±2 | Pb coat+Ni coating |
| Comparative Examples 11 | Appearance point corrosion behind the 130h | 24±2 | Chemical plating copper layer+Ni coating |
| Comparative Examples 12 | Appearance point corrosion behind the 350h | 28±10 | Resin conductive layer+Ni coating |
| Comparative Examples 13 | Appearance point corrosion behind the 370h | 25±10 | Resin conductive layer+Ni coating |
Can obviously find out from table 10～13: Comparative Examples 11 after about 130 hours, Comparative Examples 12 after 350 hours, Comparative Examples 13 all appearance point corrosions after about 370 hours; And on the other hand, for embodiment 7, even through 500 hours, under 30 power microscopes also without any a corrosion.
Embodiment 8
Make the ring shape binding magnet of 29mm (external diameter) * 25mm (internal diameter) * 5mm (height) with the method identical with embodiment 1, its performance is listed in table 15:Br=6.7kG, iHc=9.3kOe, (BH)
Max=9.5MGOe.
It is the Al of 3mm that above-mentioned bonded permanent magnet is put into oscillatory type cylinder average diameter
2O
3The ball-shape drum abrasive material seals with finishing and handles.Its process conditions and using method are with embodiment 2.
Then above-mentioned bonded permanent magnet is put into the oscillatory type cylinder carries out the dry method tumbling, use diameter to form the conductive layer that constitutes by the fine metal fragment on the bonded permanent magnet surface, see Table 14 with the fine metal fragment compression distance of porousness part and the coat thickness on Magnaglo surface on the resin surface as stub shape Fe, Ni, Co and the Cr rod of 0.5mm, long 0.4mm.Condition when tumbling is handled is with embodiment 2.
Then clean, and, carry out nickel plating afterwards with the electronickelling of nose suspension type electroplanting device.Electroplate back inner radius coating film thickness 20 μ m, outer radius is 22 μ m.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 1000 hours.Its result of the test and thicknesses of layers accuracy to size see Table 16 and table 17.
The process conditions of electroplating copper and mickel are with embodiment 2.The process conditions of zinc replacement Treatment are as follows: 40 seconds processing times, and 22 ℃ of bath temperature, the body lotion composition is: 300g/l NaOH, 40g/l zinc oxide, 1g/l iron chloride, 30g/lRossel salt.Thicknesses of layers is 0.01 μ m.Comparative Examples 14
Clean the ring shape binding magnet that obtains with embodiment 8 same methods, sealing and the surface finish carried out are afterwards similarly to Example 6 handled, and clean once more, then it are carried out electroless copper, thickness of coating 5 μ m.Under the condition identical, carry out electro-coppering and electronickelling behind the electroless copper with embodiment 8.
Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test) under the condition identical with embodiment 8, its result of the test and thicknesses of layers accuracy to size see Table 16 and table 17.The process conditions of electroless copper are with Comparative Examples 4.Comparative Examples 15
Clean the ring shape binding magnet of using method similarly to Example 6 to obtain, mixture with phenolic resins and nickel powder forms the thick electroconductive resin coat of 10 μ m in magnet surface afterwards, the magnet and the 5mm steel ball of packing in the oscillatory type cylinder then and accounting for its volume 60% are that the tumbling of carrying out under the 20mm condition 60 minutes is also polished with finishing at amplitude.
Electro-coppering and electronickelling under the condition identical then with embodiment 8, ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test) under the condition identical with embodiment 6, its result of the test and thicknesses of layers accuracy to size see Table 16 and table 17.Conduction coat treatment conditions are with Comparative Examples 5.Table 14
Table 15
Table 16
Magnetic property reduces ratio (%)=[{ (initial magnetic property)-(moisture resistivity test back magnetic property) }/(initial magnetic property)] * 100 tables 17
| Metal fragment | The compression distance that resin surface and porousness are partly located (μ m) | The coating thickness on Magnaglo surface (μ m) |
| ????Fe | ????0．5 | ????0．1 |
| ????Ni | ????0．5 | ????0．1 |
| ????Co | ????0．4 | ????0．1 |
| ????Cr | ????0．4 | ????0．1 |
| The parent material magnetic property | |||
| ????Br(kG) | ????iHc(kOe) | ???(BH) max(MGOe) | |
| Embodiment 8 Fe | ????6．9 | ????9．3 | ????9．5 |
| Embodiment 8 Ni | ????6．9 | ????9．3 | ????9．5 |
| Embodiment 8 Co | ????6．9 | ????9．3 | ????9．5 |
| Embodiment 8 Cr | ????6．9 | ????9．3 | ????9．5 |
| Comparative Examples 14 | ????6．9 | ????9．3 | ????9．5 |
| Comparative Examples 15 | ????6．9 | ????9．3 | ????9．5 |
| Before the moisture resistivity test | After the moisture resistivity test | Magnetic property reduces ratio (%) | |||||||
| Br (kG) | iHc (kOe) | (BH) max(MGOe) | Br (kG) | iHc (kOe) | (BH) max(MGOe) | Br (kG) | iHc (kOe) | (BH) max(MGOe) | |
| Embodiment 8 Fe | ?6．7 | ?9．2 | ?9．4 | ?6．6 | ?8．9 | ?9．0 | ?4．3 | ?4．3 | ?5．3 |
| Embodiment 8 Ni | ?6．7 | ?9．2 | ?9．4 | ?6．5 | ?8．9 | ?8．9 | ?5．8 | ?4．3 | ?6．3 |
| Embodiment 8 Co | ?6．6 | ?9．2 | ?9．4 | ?6．4 | ?8．8 | ?8．8 | ?7．2 | ?5．4 | ?7．4 |
| Embodiment 8 Cr | ?6．7 | ?9．2 | ?9．4 | ?6．5 | ?8．7 | ?8．8 | ?5．8 | ?6．5 | ?7．4 |
| Comparative Examples 14 | ?6．6 | ?9．1 | ?9．3 | ?6．2 | ?8．5 | ?8．5 | ?10．1 | ?8．6 | ?10．5 |
| Comparative Examples 15 | ?6．7 | ?9．1 | ?9．3 | ?6．2 | ?8．3 | ?8．4 | ?10．1 | ?10．8 | ?11．6 |
| Surface state after the moisture resistivity test | Thicknesses of layers accuracy to size (μ m) | Manufacture method | |
| Embodiment 8 Fe | No change (non-corroding) | 20±2 | Encapsulation process+Fe coat+Ni coating |
| Embodiment 8 Ni | No change (non-corroding) | 20±2 | Encapsulation process+Ni coat+Ni coating |
| Embodiment 8 Co | No change (non-corroding) | 20±2 | Encapsulation process+Co coat+Ni coating |
| Embodiment 8 Cr | No change (non-corroding) | 20±2 | Encapsulation process+Cr coat+Ni coating |
| Comparative Examples 14 | Appearance point corrosion behind the 700h | 25±2 | Encapsulation process+chemical plating copper layer+Ni coating |
| Comparative Examples 15 | Appearance point corrosion behind the 550h | 26±5 | Resin conductive layer+finishing and polishing+Ni coating |
Can find out from table 17: Comparative Examples 14 after 700 hours, Comparative Examples 15 all appearance point corrosions after 550 hours; And on the other hand,,, under 30 power microscopes, do not have the appearance point corrosion even through 800 hours for embodiment 8 yet.
Embodiment 9
Make the ring shape binding magnet of 20mm (external diameter) * 17mm (internal diameter) * 6mm (height) with the method identical with embodiment 1, its performance is as follows: Br=6.9kG, and iHc=9.4kOe, (BH)
Max=9.6MGOe.
Above-mentioned bonded permanent magnet is put into the oscillatory type cylinder carry out the dry method tumbling, use diameter to form the conductive cladding that constitutes by fine aluminium chips on the bonded permanent magnet surface as the stub shape aluminium bar of 0.8mm, long 1mm, the compression distance of fine metal fragment is about 0.9 μ m on the resin surface, and the coat thickness on Magnaglo surface is 0.5 μ m.Condition when tumbling is handled is with embodiment 1.
Then clean, carry out the zinc replacement Treatment, carry out electronickelling, electronickelling afterwards with the nose suspension type electroplanting device then.Electroplate back inner radius coating film thickness 19 μ m, outer radius is 21 μ m.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.The performance of moisture resistivity test back magnet sees Table 18, and surface appearance and thicknesses of layers accuracy to size after the moisture resistivity test see Table 19.Process conditions during electronickelling are with embodiment 1.Comparative Examples 16
Clean the ring shape binding magnet of using method similarly to Example 9 to obtain, then it is carried out electroless copper, thickness of coating 6 μ m.Under condition similarly to Example 3, electroplate copper and mickel behind the electroless copper.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.The magnetic property of moisture resistivity test back magnet sees Table 18, and surface appearance and thicknesses of layers accuracy to size after the moisture resistivity test see Table 19.The process conditions of electroless copper are with Comparative Examples 1.Comparative Examples 17
Clean the ring shape binding magnet that obtains with similarly to Example 9 method, the mixture with phenolic resins and nickel powder forms the thick conduction coat of 10 μ m in magnet surface afterwards, after this processing end, and electronickelling under the process conditions identical with embodiment 9.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.The magnetic property of moisture resistivity test back magnet sees Table 18, and surface appearance and thicknesses of layers accuracy to size after the moisture resistivity test see Table 19.The formation condition of resin conduction coat is with Comparative Examples 2.Comparative Examples 18
Clean the ring shape binding magnet of using method similarly to Example 9 to obtain, form the phenolic resin bonded layer of one deck on its surface by dipping method, then at its surface adhesion silver powder (granularity 0.7 μ m or lower), in the oscillatory type cylinder, form the thick conductive film layer of 7 μ m, electronickelling under condition similarly to Example 9 then afterwards.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.After the moisture resistivity test, the performance of magnet sees Table 18, and surface state and thicknesses of layers accuracy to size after the moisture resistivity test see Table 19.Coating forms process conditions with Comparative Examples 3.Table 18
Magnetic property reduces ratio (%)=[{ (initial magnetic property)-(moisture resistivity test back magnetic property) }/(initial magnetic property)] * 100 tables 19
| Before the moisture resistivity test | After the moisture resistivity test | Magnetic property reduces ratio (%) | |||||||
| Br (kG) | iHc (kOe) | (BH) max(MGOe) | Br (kG) | iHc (kOe) | (BH) max(MGOe) | Br (kG) | iHc (kOe) | (BH) max(MGOe) | |
| Embodiment 9 | ?6．7 | ?9．0 | ?9．2 | ?6．4 | ?8．8 | ?9．0 | ?7．2 | ?6．4 | ?6．3 |
| Comparative Examples 16 | ?6．4 | ?8．7 | ?8．9 | ?5．7 | ?7．9 | ?8．0 | ?17．4 | ?16．0 | ?16．7 |
| Comparative Examples 17 | ?6．6 | ?8．9 | ?9．3 | ?6．2 | ?8．6 | ?8．7 | ?10．1 | ?8．5 | ?9．4 |
| Comparative Examples 18 | ?6．6 | ?9．0 | ?9．2 | ?6．2 | ?8．6 | ?8．7 | ?10．1 | ?8．5 | ?9．4 |
| Surface state after the moisture resistivity test | Thicknesses of layers accuracy to size (μ m) | Manufacture method | |
| Embodiment 9 | No change (non-corroding) | 20±2 | Al coat (zinc replacement Treatment)+Ni coating |
| Comparative Examples 16 | Appearance point corrosion behind the 120h | 27±2 | Chemical plating copper layer+Ni coating |
| Comparative Examples 17 | Slight corrosion appears behind the 270h | 28±10 | Resin conductive cladding+Ni coating |
| Comparative Examples 18 | Slight corrosion appears behind the 300h | 26±10 | Conduction coat+Ni coating |
Can obviously find out from table 18 and table 19: Comparative Examples 16 after about 120 hours, Comparative Examples 17 after 270 hours, Comparative Examples 18 all appearance point corrosions after about 300 hours; And on the other hand, for embodiment 9, even through 500 hours, under 30 power microscopes also without any a corrosion.
Embodiment 10
Make the ring shape binding magnet of 36mm (external diameter) * 33mm (internal diameter) * 3mm (height) with the method identical with embodiment 1, its performance is as follows: Br=6.7kG, and iHc=9.2kOe, (BH)
Max=9.5MGOe.
With 220 such magnets is the spherical Al of 4mm with average diameter
2O
3It is 20 liters oscillatory type cylinder that the cylinder abrasive material is put into volume, and packing into accounts for the vegetable-derived materials of cylinder volume 50%, and vegetable-derived materials is that the surface is by the Al of the about 2 μ m of granularity
2O
3The juglandis,semen of the about 2mm of diameter that modification was handled carries out 150 minutes dry method surface finish then, handles with sealed airspace and finishing.
Then, magnet packed into carry out the dry method tumbling in the oscillatory type cylinder, the stub shape aluminium bar that with diameter is 0.5mm, long 0.7mm forms the conductive layer that is made of fine aluminium chips on the bonded permanent magnet surface, the degree of depth that fine fragment is pressed into resin surface is about 1.1 μ m, and the coating thickness on Magnaglo surface is 0.6 μ m.The condition that tumbling is handled is with embodiment 1.
Then clean, carry out the zinc replacement Treatment, use the electronickelling of nose suspension type electroplanting device then, carry out electronickelling afterwards.Electroplate back inner radius coating film thickness 17 μ m, outer radius is 19 μ m.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 500 hours.The performance of moisture resistivity test back magnet sees Table 20, and surface appearance and thicknesses of layers accuracy to size after the moisture resistivity test see Table 21.
The process conditions of electroplating copper and mickel are with embodiment 2.The process conditions of zinc replacement Treatment are as follows: 40 seconds processing times, and 22 ℃ of bath temperature, the body lotion composition is: 300g/l NaOH, 40g/l zinc oxide, 1g/l iron chloride, 30g/lRossel salt.Zinc displacement layer thickness is 0.01 μ m.Comparative Examples 19
Clean the ring shape binding magnet made from method similarly to Example 10, it is sealed and surface finish, clean once more, then it is carried out electroless copper, thickness of coating 6 μ m by embodiment 10.Under condition similarly to Example 10, electroplate copper and mickel behind the electroless copper.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 1000 hours.The magnetic property of moisture resistivity test back magnet sees Table 20, and surface appearance and thicknesses of layers accuracy to size after the moisture resistivity test see Table 21.The process conditions of electroless copper are with Comparative Examples 4.Comparative Examples 20
Clean the ring shape binding magnet made from method similarly to Example 10, form the thick conduction coat of 12 μ m with the mixture of phenolic resins and nickel powder in magnet surface under the following conditions afterwards.The above-mentioned magnet and the 2mm steel ball of packing in the oscillatory type cylinder then and accounting for its volume 70%, the tumbling of carrying out 90 minutes is with finishing and polishing.
Then electronickelling under the process conditions identical with embodiment 10.Ring shape binding magnet after handling is like this carried out environmental test (moisture resistivity test), 80 ℃ of temperature, relative humidity 90%, test duration 1000 hours.The performance of moisture resistivity test back magnet sees Table 20, and surface appearance and thicknesses of layers accuracy to size after the moisture resistivity test see Table 21.The process conditions of electroless copper are with Comparative Examples 5.Table 20
Magnetic property reduction ratio (%)=[((initial magnetic property)-(moisture resistivity test back magnetic property) }/(initial magnetic property)] * 100 tables 21
Can obviously find out from table 20 and table 21: Comparative Examples 19 after about 750 hours, Comparative Examples 20 all appearance point corrosions after 680 hours; And on the other hand, for embodiment 10, even through 1000 hours, under 30 power microscopes also without any a corrosion.
| Before the moisture resistivity test | After the moisture resistivity test | Magnetic property reduces ratio (%) | |||||||
| Br (kG) | iHc (kOe) | (BH) max(MGOe) | Br (kG) | iHc (kOe) | (BH) max(MGOe) | Br (kG) | iHc (kOe) | (BH) max(MGOe) | |
| Embodiment 10 | ?6．5 | ?9．0 | ?9．2 | ?6．4 | ?8．7 | ?9．0 | ?4．5 | ?5．4 | ?5．3 |
| Comparative Examples 19 | ?6．4 | ?8．7 | ?8．9 | ?6．0 | ?8．3 | ?8．5 | ?10．5 | ?9．8 | ?10．5 |
| Comparative Examples 20 | ?6．4 | ?8．9 | ?9．3 | ?6．1 | ?8．4 | ?8．5 | ?9．0 | ?8．7 | ?10．5 |
| Surface state after the moisture resistivity test | Thicknesses of layers accuracy to size (μ m) | Manufacture method | |
| Embodiment 10 | No change (non-corroding) | 18±2 | Encapsulation process+Al coat (zinc replacement Treatment)+Ni coating |
| Comparative Examples 19 | Appearance point corrosion behind the 750h | 24±2 | Encapsulation process+electroless copper+Ni coating |
| Comparative Examples 20 | Appearance point corrosion behind the 680h | 28±6 | Resin conductive cladding+finishing and polishing+Ni coating |
Commercial Application
Among the present invention, porous R-Fe-B bonded permanent magnet is carried out the dry method tumbling, wherein use the mixture of the material of polishing agent and plant origin to do polishing medium, perhaps, done polishing medium by the mixture of the material of the plant origin after the inorganic powder modification with polishing agent and surface. Can will polish powder, inorganic powder, buffing with the oily components in the material of plant origin and be bonded on the R-Fe-B base bonded magnet, fill its porous part. Also can improve bonded permanent magnet, carry out simultaneously surface finish and process. In addition, the R-Fe-B base bonded magnet is carried out the dry method tumbling in drum apparatus, do metal medium with required size, indefinite shape such as spherical, piece shape or aciculiform (linear) aluminium block, the fine fragment that aluminium is ground is pressed into porous part and the resin surface on bonded permanent magnet surface, form rete, perhaps be coated in the Magnaglo surface with the fine fragment of aluminium, thereby form one deck aluminium coating on R-Fe-B base bonded magnet surface, then the zinc replacement Treatment is carried out on the aluminium coating surface, thereby can form electrodeposited coating fine and close, that do not have pin hole, obtain having the R-Fe-B base bonded magnet of utmost point excellent corrosion resistance.
Claims (18)
1. a high corrosion-resistant R-Fe-B base bonded magnet is characterized in that the fine metal fragment is pressed into and is coated in resin surface and the porousness part that constitutes this R-Fe-B base bonded magnet surface; And this R-Fe-B base bonded magnet comprises the layer of metal clad surface, it is to apply the Magnaglo surface that constitutes described surface by the metal superfine fragment to form, and at the most surperficial formation electrodeposited coating of magnet, thereby the surface of described washing is between the two.
2. high corrosion-resistant R-Fe-B base bonded magnet, it is characterized in that sealing porousness part in the described R-Fe-B base bonded magnet surface with polishing agent powder, bonded permanent magnet buffing or the inorganic powder that also is bonded in it with the oily components in the vegetable-derived materials, the fine metal fragment is pressed into and is coated in resin surface and the described porousness part that constitutes this magnet surface; Its feature is that also this R-Fe-B base bonded magnet comprises the layer of metal clad surface, it is to apply the Magnaglo surface that constitutes magnet surface by the metal superfine fragment to form, and at the most surperficial one deck electrodeposited coating that also forms of magnet, thereby described surface metal coat is between the two.
3. according to the high corrosion-resistant R-Fe-B base bonded magnet of claim 1 or claim 2, it is characterized in that this fine metal fragment is Cu, Sn, Zn, Pb, Cd, In, Au, Ag, Fe, Ni, Co, Cr or Al, or the alloy of above element.
4. according to the high corrosion-resistant R-Fe-B base bonded magnet of claim 1 or claim 2, it is characterized in that the fine metal fragment is 0.1 μ m～2 μ m at the coating thickness that is pressed into that resin surface and porousness partly form.
5. according to the high corrosion-resistant R-Fe-B base bonded magnet of claim 1 or claim 2, it is characterized in that the fine metal fragment is 1.0 μ m or lower at the coating thickness that the Magnaglo surface forms.
6. according to the high corrosion-resistant R-Fe-B base bonded magnet of claim 5, it is characterized in that Cu, Fe, Ni, Co or Cr or their the alloy coating thickness on the Magnaglo surface is 0.2 μ m or lower.
7. according to the high corrosion-resistant R-Fe-B base bonded magnet of claim 1 or claim 2, it is characterized in that when above-mentioned fine metal fragment is aluminum or aluminum alloy, on the aluminum or aluminum alloy clad surface of described magnet surface, form a middle zinc layer, form electrodeposited coating again.
8. the manufacture method of a high corrosion-resistant R-Fe-B base bonded magnet, it is characterized in that comprising the following step: the fine metal sheet of R-Fe-B base bonded magnet and indefinite shape is packed in the drum apparatus, carry out the dry method tumbling, the fine metal fragment that grinds can be pressed into resin surface and the porousness part that constitutes R-Fe-B base bonded magnet surface, form coating, and the Magnaglo surface that constitutes this magnet surface has also applied the above-mentioned fine metal fragment of one deck, thereby, then utilize the plating outmost surface pressing formation one deck electrodeposited coating on this conductive metal coating of above-mentioned formation at this magnet surface formation layer of metal coat.
9. the manufacture method of a high corrosion-resistant R-Fe-B base bonded magnet, it is characterized in that comprising the following step: the R-Fe-B base bonded magnet is carried out the dry method tumbling, done polishing medium by the mixture of the vegetable-derived materials after the inorganic powder modification with polishing agent and vegetable-derived materials or its surface, with polishing agent powder, bonded permanent magnet buffing or also seal the porousness part on described R-Fe-B bonded permanent magnet surface with the inorganic powder of the bonding of the oily components in the vegetable-derived materials, and finishing and improve its surface; In the fine metal sheet and the drum apparatus of packing into this bonded permanent magnet and indefinite shape, carry out the dry method tumbling, so that the fine metal fragment that grinds can be pressed into the resin surface and the described porousness part of this magnet surface, form coating, and the Magnaglo surface of this magnet surface also applied one deck fine metal fragment, thereby makes the surface of this R-Fe-B base bonded magnet have conductivity; Follow the most surperficial formation one deck electrodeposited coating at magnet.
10. according to Claim 8 or the high corrosion-resistant R-Fe-B base bonded magnet manufacture method of claim 9, it is characterized in that this fine metal fragment is Cu, Sn, Zn, Pb, Cd, In, Au, Ag, Fe, Ni, Co, Cr or Al, or the alloy of above element.
11. according to Claim 8 or the high corrosion-resistant R-Fe-B base bonded magnet manufacture method of claim 9, it is characterized in that when above-mentioned fine metal fragment is aluminium, on the surface of the aluminium coating of described magnet surface, form one with the zinc replacement Treatment in the middle of the zinc layer, form electrodeposited coating again.
12. according to Claim 8 or the high corrosion-resistant R-Fe-B base bonded magnet manufacture method of claim 9, the fine metal sheet that it is characterized in that this indefinite shape is spherical, piece shape or aciculiform, and size is 0.1mm～10mm.
13. according to the high corrosion-resistant R-Fe-B base bonded magnet manufacture method of claim 12, it is characterized in that Cu, Fe, Ni, Co or the Cr fine metal sheet of this indefinite shape is sphere, piece shape or aciculiform, size is 0.1mm～5mm.
14. according to Claim 8 or the high corrosion-resistant R-Fe-B base bonded magnet manufacture method of claim 9, it is characterized in that the fine metal chip length that tumbling grinds is 5 μ m or littler.
15. according to Claim 8 or the high corrosion-resistant R-Fe-B base bonded magnet manufacture method of claim 9, use rotary, oscillatory type or centrifugal cylinder when it is characterized in that tumbling, the volume ratio of above-mentioned magnet and above-mentioned fine metal fragment (magnet/fine metal fragment) is 3 or lower.
16., it is characterized in that polishing agent is Metal Ball or the inorganic powder polish abrasive firing and harden according to the high corrosion-resistant R-Fe-B base bonded magnet manufacture method of claim 9.
17., it is characterized in that above-mentioned vegetable-derived materials is plant shell, wood chip, pericarp or maize cob according to the high corrosion-resistant R-Fe-B base bonded magnet manufacture method of claim 9.
18. according to Claim 8 or the high corrosion-resistant R-Fe-B base bonded magnet manufacture method of claim 9, it is characterized in that above-mentioned R-Fe-B base bonded magnet and above-mentioned fine metal fragment carry out the dry method tumbling under inert gas atmosphere.
Applications Claiming Priority (20)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP316435/1997 | 1997-10-30 | ||
| JP31643597 | 1997-10-30 | ||
| JP33368197 | 1997-11-17 | ||
| JP333681/1997 | 1997-11-17 | ||
| JP04455898A JP3236813B2 (en) | 1997-10-30 | 1998-02-10 | High corrosion resistance R-Fe-B bonded magnet and method for producing the same |
| JP44558/1998 | 1998-02-10 | ||
| JP04455998A JP3236814B2 (en) | 1997-11-17 | 1998-02-10 | High corrosion resistance R-Fe-B-based bonded magnet and method for producing the same |
| JP44559/1998 | 1998-02-10 | ||
| JP48828/1998 | 1998-02-12 | ||
| JP04882898A JP3236816B2 (en) | 1998-02-12 | 1998-02-12 | High corrosion resistance R-Fe-B bonded magnet and method for producing the same |
| JP48827/1998 | 1998-02-12 | ||
| JP04882798A JP3236815B2 (en) | 1998-02-12 | 1998-02-12 | High corrosion resistance R-Fe-B bonded magnet and method for producing the same |
| JP10056044A JPH11238641A (en) | 1998-02-19 | 1998-02-19 | Highly corrosion resistant r-fe-b bonded magnet and its manufacture |
| JP56044/1998 | 1998-02-19 | ||
| JP83012/1998 | 1998-03-12 | ||
| JP10083012A JPH11260614A (en) | 1998-03-12 | 1998-03-12 | Anticorrosive r-fe-b bonded magnet and manufacture of the same |
| JP10083011A JPH11260613A (en) | 1998-03-12 | 1998-03-12 | Anticorrosive r-fe-b bonded magnet and manufacture of the same |
| JP83011/1998 | 1998-03-12 | ||
| JP103496/1998 | 1998-03-30 | ||
| JP10103496A JPH11283818A (en) | 1998-03-30 | 1998-03-30 | High corrosion-resistant r-fe-b bonded magnet and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1279810A true CN1279810A (en) | 2001-01-10 |
| CN1205626C CN1205626C (en) | 2005-06-08 |
Family
ID=27579948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB988114569A Expired - Lifetime CN1205626C (en) | 1997-10-30 | 1998-10-23 | High corrosion-resistant R-Fe-B-base bonded magnet and method of manufacturing the same |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1028437B1 (en) |
| KR (1) | KR100374398B1 (en) |
| CN (1) | CN1205626C (en) |
| DE (1) | DE69834567T2 (en) |
| WO (1) | WO1999023675A1 (en) |
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| CN103403821A (en) * | 2011-03-02 | 2013-11-20 | 日立金属株式会社 | Rare-earth bond magnet manufacturing method |
| CN103632687A (en) * | 2013-12-19 | 2014-03-12 | 广东金潮集团有限公司 | CD (Compact Disc) optical disk electroplating material |
| CN103779027A (en) * | 2014-01-27 | 2014-05-07 | 江西江钨稀有金属新材料有限公司 | Cohesive rare earth magnetic powder and preparation equipment thereof |
| CN105810380A (en) * | 2016-03-11 | 2016-07-27 | 江西江钨稀有金属新材料有限公司 | High-temperature resistant and high-magnetism rear earth permanent magnetic material and preparation method thereof |
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| JP3278647B2 (en) | 1999-01-27 | 2002-04-30 | 住友特殊金属株式会社 | Rare earth bonded magnet |
| JP3389193B2 (en) | 1999-04-26 | 2003-03-24 | 住友特殊金属株式会社 | Method for Sealing Holes in Ring-Shaped Bonded Magnet and Ring-Shaped Bonded Magnet Sealed by the Method |
| JP2001073198A (en) * | 1999-07-01 | 2001-03-21 | Sumitomo Special Metals Co Ltd | Device for electroplating and electroplating method using this device |
| US6866765B2 (en) | 2000-07-07 | 2005-03-15 | Hitachi Metals, Ltd. | Electrolytic copper-plated R-T-B magnet and plating method thereof |
| FR2819120B1 (en) * | 2000-12-28 | 2003-02-28 | Valeo Equip Electr Moteur | METHOD FOR MANUFACTURING AN INDUCTOR OF A ROTATING ELECTRIC MACHINE |
| US7449100B2 (en) | 2001-10-29 | 2008-11-11 | Hitachi Metals, Ltd. | Method for forming electroplating film on surfaces of articles |
| JP4162884B2 (en) * | 2001-11-20 | 2008-10-08 | 信越化学工業株式会社 | Corrosion-resistant rare earth magnet |
| US8717132B2 (en) | 2012-01-09 | 2014-05-06 | Apple Inc. | Unibody magnet |
| CN113589594B (en) * | 2021-07-19 | 2022-07-12 | Tcl华星光电技术有限公司 | Display panel and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62290107A (en) * | 1986-06-09 | 1987-12-17 | Seiko Instr & Electronics Ltd | Magnet |
| JPH0254504A (en) * | 1988-08-18 | 1990-02-23 | Nippon Steel Corp | Highly corrosion-resistant rare earth permanent bonded magnet and manufacture thereof |
| DE69220519T2 (en) * | 1991-03-04 | 1998-02-19 | Toda Kogyo Corp | Process for plating a bonded magnet and bonded magnet with a metal coating |
| JP3151843B2 (en) * | 1991-03-04 | 2001-04-03 | 戸田工業株式会社 | Alloy magnet plating method |
| JPH08250356A (en) * | 1995-03-13 | 1996-09-27 | Daido Steel Co Ltd | Alloy powder for anisotropic magnet, anisotropic permanent magnet using the same and manufacture thereof |
-
1998
- 1998-10-23 WO PCT/JP1998/004829 patent/WO1999023675A1/en active IP Right Grant
- 1998-10-23 CN CNB988114569A patent/CN1205626C/en not_active Expired - Lifetime
- 1998-10-23 EP EP98950380A patent/EP1028437B1/en not_active Expired - Lifetime
- 1998-10-23 DE DE69834567T patent/DE69834567T2/en not_active Expired - Lifetime
- 1998-10-23 KR KR10-2000-7004631A patent/KR100374398B1/en not_active IP Right Cessation
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103403821A (en) * | 2011-03-02 | 2013-11-20 | 日立金属株式会社 | Rare-earth bond magnet manufacturing method |
| CN103403821B (en) * | 2011-03-02 | 2016-08-10 | 日立金属株式会社 | The manufacture method of rare-earth bond magnet |
| CN103632687A (en) * | 2013-12-19 | 2014-03-12 | 广东金潮集团有限公司 | CD (Compact Disc) optical disk electroplating material |
| CN103779027A (en) * | 2014-01-27 | 2014-05-07 | 江西江钨稀有金属新材料有限公司 | Cohesive rare earth magnetic powder and preparation equipment thereof |
| CN106782979A (en) * | 2014-01-27 | 2017-05-31 | 江西江钨稀有金属新材料股份有限公司 | A kind of binding type rare-earth magnetic and its Preparation equipment |
| CN105810380A (en) * | 2016-03-11 | 2016-07-27 | 江西江钨稀有金属新材料有限公司 | High-temperature resistant and high-magnetism rear earth permanent magnetic material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69834567T2 (en) | 2007-04-26 |
| CN1205626C (en) | 2005-06-08 |
| DE69834567D1 (en) | 2006-06-22 |
| EP1028437A4 (en) | 2001-06-13 |
| WO1999023675A1 (en) | 1999-05-14 |
| KR100374398B1 (en) | 2003-03-04 |
| EP1028437A1 (en) | 2000-08-16 |
| EP1028437B1 (en) | 2006-05-17 |
| KR20010040267A (en) | 2001-05-15 |
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Correction item: Priority Correct: 1998.03.30 JP 103496/1998 False: No tenth priorities Number: 23 Page: The title page Volume: 21 |
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| COR | Change of bibliographic data |
Free format text: CORRECT: PRIORITY TO: 1998.3.30 JP 103496/1998 |
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| ERR | Gazette correction |
Free format text: CORRECT: PRIORITY; FROM: NONE NO. 10 PRIORITY TO: 1998.3.30 JP 103496/1998 |
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| CI01 | Correction of invention patent gazette |
Correction item: Priority Correct: 1998.3.30 JP 103496/1998 False: Lack of tenth priorities Number: 23 Page: 682 Volume: 21 |
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| CI03 | Correction of invention patent |
Correction item: Priority Correct: 1998.3.30 JP 103496/1998 False: Lack of tenth priorities Number: 23 Page: The title page Volume: 21 |
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| COR | Change of bibliographic data |
Free format text: CORRECT: PRIORITY; FROM: LACK NO. 10 PRIORITY TO: 1998.3.30 JP 103496/1998 |
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| ERR | Gazette correction |
Free format text: CORRECT: PRIORITY; FROM: LACK NO. 10 PRIORITY TO: 1998.3.30 JP 103496/1998 |
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| CX01 | Expiry of patent term |
Granted publication date: 20050608 |
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| CX01 | Expiry of patent term |