CN1958871A - Plating tool, plating method, electroplating apparatus, plated product, and method for producing plated product - Google Patents
Plating tool, plating method, electroplating apparatus, plated product, and method for producing plated product Download PDFInfo
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- CN1958871A CN1958871A CN 200610136180 CN200610136180A CN1958871A CN 1958871 A CN1958871 A CN 1958871A CN 200610136180 CN200610136180 CN 200610136180 CN 200610136180 A CN200610136180 A CN 200610136180A CN 1958871 A CN1958871 A CN 1958871A
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Abstract
The invention provides a plating technique for preventing the generation of rust and blisters and further efficiently performing film deposition in a plated product of a rare earth bond magnet. A plating method for depositing a nickel film on the surface of a rare earth bond magnet by electrochemical reaction is disclosed and includes: a step wherein a nickel film of a single layer is deposited using a plating bath containing nickel sulfate, nickel chloride and boric acid; and a surface activation step wherein, before the plating step, a rare earth bond magnet as the object to be plated is dipped into a hydrochloric acid with a concentration of 1 to 6% for 7 to 25 s, and is subjected to surface treatment.
Description
Technical field
The present invention relates to plating tool, solution and coating method and electroplanting device, specifically, relate to plating tool, solution and coating method and electroplanting device under the hard disk that is applicable to for example computer carries out plating as plated body with employed ringshaped magnets such as motor etc. the situation.
In addition, the present invention relates to the manufacture method and the plated product of solution and coating method, plated product, specifically, relate to solution and coating method and the manufacture method of plated product and the plated product that utilizes this manufacture method to make that forms the nickel overlay film on the surface of rare-earth bond magnet.
In addition, the present invention relates to electro-plating method and electroplanting device, specifically, the generation that relates to the pin hole that can prevent the plated body surface also can form the electro-plating method of even and fine and close overlay film and realize its electroplanting device.
Background technology
When electroplating as the plated body of smaller types such as employed ringshaped magnet such as motor, can utilize following method to carry out plating, promptly, a plurality of plated bodies of in the container that is called as cylinder (barrel), packing into, with cathode arrangement in cylinder, make on one side the cylinder rotation, implement " the cylinder plating method " of plating on one side or plated body is hung on the hanger of double as negative electrode and " the rack plating method " of enforcement plating.
But, use the plating method of cylinder owing to can't control plated body respectively, therefore the problem that is easy to generate the inequality of thickness in each batch for each plated product is arranged.In addition, in each plated product, also can't obtain the thickness of homogeneous, often produce the inequality of thickness because of the difference at position.In addition, under the lower situation of the toughness (intensity) of plated body, be easy to generate crackle, thereby cause production of foreign matters easily.Use in the plating method of hanger, easy residual hanger trace on plated product, thus the problem that can't obtain homogeneous and fine and close plating is arranged.
So, proposed respectively relevant for the cylinder plating method improving technology (for example No. 3021728 communiques of patent), about the improving technology of rack plating method (for example with reference to the spy open the 2001-131800 communique, the spy opens the 2001-152388 communique) etc.
Though it is to utilize the swing of instrument integral body to make the instrument of Workpiece Rotating that the spy opens the plating tool of 2001-131800 communique, because with the speed of rotation of uncontrollable each workpiece of this mode, so the thickness inhomogenous problem that becomes is arranged.In addition, the separating out composition (for example nickel) and can stick to the electrode part of plating tool of plating liquid, thereby also must have the problem of thickness attenuation.Open the situation of the plating tool of 2001-152388 communique for the spy, though the rotation Be Controlled of workpiece, but, because the insulation spacer block is arranged in configuration between each workpiece of bracing member shape, therefore compare with the thickness of the periphery of having made the cyclic workpiece, have the problem that end face or inner peripheral surface become shade.That is, because therefore the gap of the end face of uncontrollable workpiece and insulation spacer block is easy to carry out plating under a certain side's of deflection state, thereby is for example producing film thickness difference between both ends of the surface.In addition, owing to be the mode of a plurality of cyclic workpiece of suit on bar-shaped bracing member, therefore location and disassembling section are very numerous and diverse, need the more operating time of cost, thereby the low problem of operation efficiency is arranged.
In addition, in recent years, in the plating of electronic unit etc., the precision that special requirement are higher promptly, requires to form homogeneous and fine and close overlay film.Particularly, when plated body forms the shape with inner peripheral surfaces such as ring-types, the problem that it is extremely thick that the thickness that has an inner peripheral surface that becomes electric shade becomes as thin as a wafer or the thickness of end face becomes and so on.As countermeasure, proposed in the hollow bulb of plated body, to have set the scheme (for example the spy opens the 2001-73198 communique) of the plating tool of supplementary anode with hollow bulb at this problem.But, when anode is the material of easy stripping, has anode self and partly peel off and come off, thereby cause the problem of production of foreign matters.
In addition, therefore rare-earth bond magnet be exactly the material that is easy to generate iron rust owing to the iron that contains more ratio as magneticsubstance originally.In addition, owing to be and the matrix material of resin,, also be easy to produce iron rust, expansion even therefore implement and the plating program identical to the plating of general metal.In addition,, therefore be easy to generate pin hole, in this, also can be described as the material that is not suitable for plating owing to more emptying aperture is arranged on the surface of rare-earth bond magnet.
In order on this kind rare-earth bond magnet, to form good plating, propose to have the method for carrying out base treatment.As base treatment, for example can enumerate following method, promptly, after implementing electroless plating or having brushed the mixture of resin and conductive material, carry out electric plating method (spy opens flat 4-276095 communique (scope of claim etc.)), at powder and the grinding chip of binding magnet and the hollow hole part of inorganic powder filled rare-earth bond magnet with abrasive substance, utilize the grease partial fixing of vegetalitas medium, behind the sealing of hole, with Cu microplate covering surfaces, form the method (spy opens flat 11-204321 communique (scope of claim etc.)) of electrolytic coating, at powder and the grinding chip of binding magnet and the hollow hole part of inorganic powder filled rare-earth bond magnet with abrasive substance, utilize the grease partial fixing of vegetalitas medium, behind the sealing of hole, with Al microplate covering surfaces, form the method (spy opens flat 11-283818 communique (scope of claim etc.)) of electrolytic coating.
On the other hand, in nickel plating, though using the method for the watt bath that contains single nickel salt, nickelous chloride and boric acid is general method, but in order to prevent to produce iron rust, proposition has in the plating of R-Fe-B class binding magnet, uses not the method for the nickel plating bath of chloride ion-containing (No. 3232037 communique of patent (0036 section etc.)).
The base treatment of conventional art only its processing just needs multistage operation etc., thereby very complicated, and efficient is relatively poor, is the method that is not suitable for plant-scale enforcement.In addition, the result of complex procedures is, is difficult to make the base treatment success, can cause on the contrary expanding or film forming unequal.Particularly, when base treatment layer and magnet main body connect airtight power hour, cause easily and expand or the unequal problem of film forming.
In addition, when the plating of rare-earth bond magnet, remove and sensitization, before plating, carry out surface treatment (acid activityization) for the oxide film that it is surperficial.As surface treatment agent because consider if on the more rare-earth bond magnet of emptying aperture the residual chlorine ion, then can cause iron rust, therefore do not use hydrochloric acid, for example use sulfuric acid.But, sulfuric acid for firm oxide film to remove effect lower, thereby have surface activation to handle long shortcoming of required time.
In plating, as one of reason of tiny flaw that causes plating (pin hole) or iron rust, the metal species foreign matters such as magnetic chip that are present in the plating bath can become problem attached to the phenomenon on the plated body (workpiece).In addition, in order from plating bath, to remove the metal species foreign matter, adopt plating bath is filtered or the method for centrifugation.In addition, for same purpose, proposition has a plurality of magnet with magnetic flux of 900 Gausses of configuration in coating bath, the magnetic chip is adsorbed on the magnet and the method for removing from plating bath (is for example opened (0015 section in flat 5-306500 communique with reference to the spy, Fig. 1)) or form the bottom of dual plastic coating bath, set magnet, make the metal species foreign matter, thereby prevent the technology (for example opening flat 9-3694 communique (Fig. 1)) of the suspension in plating bath with reference to the spy attached to the bottom.
As mentioned above, in the past as the reason that causes pin hole or iron rust in plating, the metal species foreign matter has been realized corresponding with it solution as problem.But the inventor etc. have carried out detailed research to the formation of pin hole, found that, and be the metal species foreign matter form the reason of pin hole, not equal to be organic class foreign matter such as epidermis sheet.
Particularly in plating, because organic class foreign matter is compared with plated body and plating, resistance value is very big, so this part can't form plating, and the result will produce pin hole.So, will damage widely as originally by plating should additional function attractive in appearance, environment resistant, resistance to chemical reagents etc.And owing to contain the element that chlorine, sulphur etc. bring out iron rust easily in organic class foreign matter, therefore the danger that partly produces iron rust by pin hole is higher than the pin hole that causes because of other reasons.In this, situation for the metal species foreign matter of electroconductibility such as magnetic chip, even owing to adhere to, also can form overlay film according to the mode that it is imbedded, the infringement homogeneity even therefore on overlay film, produce concavo-convex, but seldom can become the reason that directly causes iron rust to produce, thus compare with organic class foreign matter, less to the influence of plating quality.
Though the organic class foreign matter in the plating bath can utilize the plating operation in dust free chamber or the clean completely of whole plating program be waited reduce,, these methods can produce bigger cost burden to product.
Summary of the invention
One of purpose of the present invention is, is provided at when the high electronic unit of plating accuracy requirement etc. carried out plating, can form plating tool and electroplanting device fine and close and overlay film uniformly on plated body.
Two of purpose of the present invention is, is provided at when the high electronic unit of plating accuracy requirement etc. carried out plating, and operability is good and can form plating tool and electroplanting device fine and close and overlay film uniformly on plated body.
Three of purpose of the present invention is the coating technology that is provided for preventing the generation of iron rust or pin hole in advance in the plated product of rare-earth bond magnet and forms overlay film expeditiously.
Four of purpose of the present invention is, provides by effectively and at low cost removing organic class foreign matter in the plating bath and prevents the technology of formation of the pin hole of plating.
In order to solve described problem, mode one of the present invention is the plating tool with following feature, promptly, have the peristome that on the supporter that rotates freely, runs through formation, stride the transversal established, promote the plating bath guidance part of the inflow of plating bath according to the mode of transverse openings respectively towards described peristome at the two ends of described peristome, will be by the space that inner-wall surface and described transversal marked of described peristome as the room that dispose plated body respectively.
According to the invention of this plating tool, will be by the space that inner-wall surface, transversal marked of peristome as the room of individual configuration plated body separately.Use in the plating of tool drum in the past, because can not moving at each plated body of cylinder inner control, therefore can't obtain uniform thickness, thereby the problem that thickness inequality on each product or each position is arranged, but, plating tool of the present invention is not only constructed simple and easy, and carries out the film thickness monitoring of the overlay film of plated product easily, can prevent the inequality of thickness.In addition owing to can in plating, not clash between the plated body as the plating that utilizes tool drum to carry out, even so the lower material of toughness, also be difficult to crack.And, by the plating bath guidance part of the inflow that promotes plating bath is set, as described later shown in the embodiment, can promote the renewal of the plating bath in the described room, quicken the formation of overlay film, improve plating efficient, can also improve simultaneously the inequality of thickness greatly, thereby obtain overlay film more uniformly.
Mode two of the present invention is the plating tools with following feature, promptly, have the peristome that on the supporter that rotates freely, runs through formation, stride the transversal of establishing, the containment wall that dwindles the opening surface of described peristome according to the mode of transverse openings respectively at the two ends of described peristome, will be by the space that inner-wall surface and described transversal marked of described peristome as the room of individual configuration plated body separately.
According to the invention of this plating tool, as described later shown in the embodiment, dwindle the containment wall of peristome by setting, the inequality of thickness can be improved greatly, thereby overlay film more uniformly can be obtained.
In addition, because the room is located on the supporter that rotates freely, so plated body can be accompanied by the rotation of this supporter and moves in the room.So, can be as the rack plating instrument yet, residual tool mark on plated product.
Mode three of the present invention is the plating tools with following feature, promptly, have the peristome that on the supporter that rotates freely, runs through formation, stride the transversal established, and the wall body that form outstanding from opening edge portion according to the mode of transverse openings respectively towards the opening surface of described peristome at the two ends of described peristome, will be by the space that inner-wall surface and described transversal marked of described peristome as the room of individual configuration plated body separately.According to the invention of this plating tool, can obtain the action effect identical with mode 2.
Mode four of the present invention is the plating tools that also have following feature in mode two or three,, has the plating bath guidance part that promotes the inflow of plating bath towards described peristome that is.According to the invention of this plating tool, except the action effect identical,, can promote the renewal of the plating bath in the described room by the plating bath guidance part of the inflow that promotes plating bath is set with mode two or three, prevent the reduction of plating efficient.
Mode five of the present invention is the plating tools that also have following feature in mode one or four, that is, described plating bath guidance part is by constituting making the end difference lower than described supporting body surface around the described peristome.According to the invention of this plating tool, except having the action effect identical, for example, can promote the inflow of plating bath with easy structure by being provided with making the end difference lower around the peristome than the surface of supporter with mode one or four.
Mode six of the present invention is the plating tools that also have following feature in mode one or four, that is, described plating bath guidance part is by constituting with mortar shape unfolded inclined-plane from the surface of described peristome towards described supporter.According to the invention of this plating tool, except having the action effect identical,, just can promote the inflow of plating bath with easy structure by being provided with from peristome towards the surface of supporter with mortar shape unfolded inclined-plane with mode one or four.
Mode seven of the present invention is the plating tools that also have following feature in any from mode one to six, that is, described transversal double as provides the electrode of electric current to plated body.According to the invention of this plating tool, except having any identical action effect with from mode one to six, because therefore transversal double as electrode can make the formation of plating tool oversimplify.In addition, in plating, can follow the counter-rotating of the supporter of rotation, the plated body in the room is also reversed, make it to contact with the electrode of opposition side, in addition, even in plating bath, under the situation of plated body come-up, also can make it to contact with the electrode of upside.So, just can in roughly whole periods of whole plating time, guarantee state to the plated body energising, carry out good overlay film and form.In addition, replace owing to the face of the plated body that contacts with electrode is accompanied by the counter-rotating action, so also can control the thickness on two sides equably.In addition, the film defective of because single face Long contact time electrode only, therefore plating and electrode set can not take place yet, peeling off and so on.
Mode eight of the present invention is the plating tools that also have following feature in any from mode one to seven, promptly, described room has the rotation that is accompanied by described supporter and two settling positions that the plated body that moves in the room stably supports within a certain period of time at least, to the way that another settling position moves, plated body contacts with at least 1 contact site of the inner-wall surface in described room at the settling position of plated body in the middle of these at least two settling positions.Invention according to this plating tool, except having any identical action effect with from mode one to seven, by adopt the settling position of plated body in the room when another settling position moves with the structure that contacts avoided in room, the rotation of certain orientation just can be provided to plated body with simple formation.In addition, can also utilize the shape in room easily to carry out control to the rotation amount of plated body.
Mode nine of the present invention is the plating tools that also have following feature in mode eight, promptly, no matter which turned position described supporter moves to, and the shape in described room also remains the shape that the line that connects a described settling position and described another settling position can not overlap with vertical direction.Invention according to this plating tool, except having the action effect identical with mode eight, can also easily produce, in the rotational action of supporter, plated body is at the structure that contacts with the wall in room to the way that another settling position moves from a settling position because of gravity, thereby the rotation of certain orientation can be provided to plated body.
Mode ten of the present invention is the plating tools that also have following feature in any from mode one to nine, that is, a plurality of described rooms are arranged and are arranged on the described supporter.According to the invention of this plating tool, except having any identical action effect with from mode one to nine, by on supporter, arranging a plurality of rooms, can 1 time a plurality of plated bodies be handled.So, in room that plated body is packed into respectively, can be under the state of the control of carrying out thickness, correspondence is carried out the processing of a greater number.
Mode 13 of the present invention is the plating tools that also have following feature in any from mode one to 12, that is, described supporter constitutes by forming along the long plate of radius of gyration direction.Invention according to this plating tool, except having any identical action effect with from mode one to 12, because supporter is made along the long plate shape of radius of gyration direction, and it is big that the circumference of rotation becomes, thereby can guarantee the agitating function of plating bath fully.
Mode 14 of the present invention is the plating tools that also have following feature in any from mode one to 13, that is, be that the center is with a plurality of described supporters of radial formation with the rotation axis.In the invention of this plating tool, except having any identical action effect with from mode one to 13 since with the rotation axis be the center with a plurality of supporters of radial formation, therefore can further improve the agitating function of plating bath.In addition, can also handle thereby can more effectively carry out plating corresponding to the processing of a greater number.
Mode 18 of the present invention is the plating tools that also have following feature in mode 17, that is, described support portion is that being located at described rotation axis is projection on the base portion of center of rotation.In this mode two, owing to the support portion is formed as projection, therefore except the action effect of acquisition mode 17, the loading and unloading of plated body are more prone to, and can carry out plating effectively and handle.
Mode 19 of the present invention is the plating tools that also have following feature in mode 18, that is, be to have arranged a plurality of described support portions on the central circular at the described rotation axis with described base portion.In this mode 18,, therefore except the action effect of mode 18, can also once handle a plurality of plated bodies owing on circle, arranged a plurality of support portions.So, by plated body being hung on each support portion, can be in the control of carrying out the plating thickness, correspondence is carried out the processing of a greater number.
In addition, condition approximate equality ground such as the electric field that can also be subjected in plating bath plated body, fluid resistance distribute.
In addition,, the effect of stirring plating bath is arranged also, handle thereby can carry out plating effectively by the revolution of a plurality of support portions.
Mode 22 of the present invention is the plating tools that also have following feature in mode 21, that is, the diameter of described plectane is set to littler than the internal diameter of plated body.In the plating tool of this mode 22, except having the action effect identical with mode 21, the diameter by making plectane can not can separate plectane and support portion or support portion and base portion ground and hangs plated body less than the internal diameter of plated body, therefore the location is easier, and processing efficiency is improved.
Mode 24 of the present invention is the solution and coating method that the cyclic plated body carried out plating with any one plating tool of use from mode 17 to 23.According to the solution and coating method of mode 24, can obtain from mode 17 to mode any identical action effect 23 and carry out plating.Particularly, owing to can carry out the film thickness monitoring of plating, therefore can make high-precision ring-type plated product as precise part.
According to this solution and coating method, the surface activation of the specified time that utilization is carried out with the hydrochloric acid of specific concentrations is handled and is used the overlay film of the individual layer of the plating bath (watt is bathed) that contains single nickel salt, nickelous chloride and boric acid to form, and can obtain to have suppressed the second best in quality plating that iron rust and expansible produce.Particularly, by adopting surface treatment time of 7～25 seconds, can be when giving full play to the oxide film that utilizes hydrochloric acid and removing effect, the detrimentally affect of avoiding the oxidation etc. of rare-earth bond magnet self to cause by acid treatment.
Mode hentriaconta-of the present invention is the solution and coating method that also has following feature in mode 30, that is, described plating bath is the plating bath that contains the semi-gloss additive.According to this mode hentriaconta-, in the action effect of keeping mode 30, can carry out the semi-gloss plating.In addition, the semi-gloss additive do not contain might be relevant with the corrosion of magnet raw material sulphur, therefore can also expect has the effect that prevents indenture (pit), can form good overlay film by adding it.
Mode 32 of the present invention is the manufacture method that formed the plated product of nickel overlay film on the surface of rare-earth bond magnet, it is manufacture method with plated product of following feature, promptly, as described rare-earth bond magnet, use the rare-earth bond magnet of void content below 7 volume %, in the hydrochloric acid that this rare-earth bond magnet is immersed in 1～6% concentration 7～25 seconds and carried out after the surface treatment, the plating bath that contains single nickel salt, nickelous chloride and boric acid by use is electroplated, and forms the nickel overlay film of individual layer.In this mode 32, can make and have good plating and the good nickel plating product of solidity to corrosion.In addition, by using the rare-earth bond magnet of void content below 7 volume %, especially can obtain the plated product that has prevented that iron rust and expansible from producing.
The coating effect of the ferromagnetic powder that produces, the filling effect (compactness) of magnet itself, thereby the rust-preventing characteristic of rare-earth bond magnet itself improves.So,, can provide good quality to the plated product of rare-earth bond magnet with the good solidity to corrosion of bringing by plating.
Mode hentriaconta-of the present invention is that the plated body surface in plating bath utilizes electrochemical reaction to form the electro-plating method of plating, it is electro-plating method with following feature, that is, surface magnetic flux density is carried out plating in the magnet configuration more than 0.25 tesla in described plating bath.
Cause the pin hole of plating and organic class foreign matter of iron rust, in most of the cases can in plating bath, suspend, judge attached on the plated body (workpiece) with state with metal species foreign matter formation one.According to electro-plating method of the present invention,, just can make the organism-metal combination that exists as foreign matter in the plating bath by magnet absorption, seizure by surface magnetic flux density is carried out plating in the magnet configuration more than 0.25 tesla in described plating bath.Like this, just can prevent the pin hole formation of plating or the generation of iron rust.On the other hand, for organic class foreign matter of containing metal class foreign matter not, though they in plating bath, exist since can be as metal cationization, so in electroplating work procedure, can electro-adsorption on plated body.So the plating of gained just becomes the film with homogeneous and fine and close advantage, in requiring high-precision industrial circle, can provide possessed resistance to chemical reagents, the plated product of environment resistant, high reliability.In addition, electro-plating method of the present invention is owing to being to utilize magnetic force to remove the method for foreign matter, and is therefore also very effective in the eutectoid plating of the filtration difficulty that makes plating bath round-robin mode.And in the present invention, " plating " speech uses to comprise the meaning that flows into electro-deposition painted broad.
Mode 32 of the present invention is that the plated body surface in plating bath utilizes electrochemical reaction to form the electro-plating method of plating, it is electro-plating method with following feature, that is, the magnet configuration that will have the surface magnetic flux density that can catch the fine organism-metal combination that suspends in plating bath is in described plating bath and carry out plating.
According to the invention of this electro-plating method, can obtain the action effect identical with the mode hentriaconta-.
This electroplanting device is to be the device that is fit on the solution and coating method of embodiment 31.
In plating, on plating, adhere to organic reason and roughly think there are 2.
The first, under the situation of organic class foreign matter and plated body physical adsorption, this can enumerate this foreign matter and plated body mechanical bond (extension), bonding etc.For this situation, utilize the amount of agitation of the plating bath in the coating bath or stirring means, to the pre-treatment that utilizes alkali of plated body, in most of the cases can solve.
It two is, has adhered under the state of micro-metal on organic class foreign matter, is subjected to the electric attraction of plated body, the situation of absorption.Research according to inventor etc., the surface of organic class foreign matter of reason that becomes iron rust is owing to generally be made of the fine curved surface of complexity, with the situation of metallic joint such as magnetic chip under, this bonding force is bigger, utilizes aforesaid means to be not easy to remove this combination.Therefore, be identified at this state and in plating bath, suspend, on plated body (workpiece).At this moment, the shared ratio of the metal species foreign matter that engages with organic class foreign matter is big more, and the possibility that then is adsorbed on the plated body is just high more.
Figure 26 is the figure that illustrates the cross section of the pin hole part 71 that is formed by foreign matter of taking with electron microscope.In figure, symbol 461 is coating surfaces, and symbol 463 is plating (cross sections), and symbol 473 is foreign matters.Can judge that from Figure 26 the part of having adhered to foreign matter 473 can't form plating, form the space and become pin hole with the shape of being out of shape.Though foreign matter 473 is the states that are embedded in as chock in the plating 463, owing to contact with workpiece 405, therefore quilt is furthered and is adhered to workpiece 405 in the forming process of plating 463.
In addition, the results of elemental analyses of expression foreign matter 473 parts among Figure 27.Shown in figure, from foreign matter, with metallic element (Ni; Precipitating metal) together, C, S, O, Cl etc. have been detected from organic element (and Si is for measuring the basis).In addition, with this ultimate analysis, also utilize FT-IR and raman spectroscopy to measure and carried out organic Analysis and Identification.Confirm that thus foreign matter is the combination of organism and metal, organism is small lamellar bodies such as epidermis.
Can see that from above situation for the pin hole that prevents plated body forms and the generation of iron rust, it is effective that efficient is removed the organism-metal combination that suspends goodly in plating bath.Therefore this organism-metal combination has the character that is adsorbed on the magnet owing to contain metal.But under the inadequate situation of the magnetic force of magnet, adsorbed organism-melts combine is known from experience because of plating bath liquid stream etc. and is broken away from magnet once more.For example, open shown in the flat 5-306500 communique as the spy, 900 Gausses (0.09 tesla) though about the magnet of surface magnetic flux density can keep adsorbed state for metal species foreign matters such as magnetic chips, can not keep adsorbed organic matter-metal combination always.In addition, for example the spy opens shown in the flat 9-3694 communique, press from both sides betwixt every the next door and under the situation of distributed magnet, owing to need guarantee the intensity of coating bath, need certain wall thickness, magnet density in the plating bath can reduce greatly, even therefore can catch the metal species foreign matter, but also can not catch organism-metal combination.
In contrast, as described later shown in the embodiment 5, when the surface magnetic flux density of magnet was above in 0.25 tesla, the organism-metal combination that is adsorbed on the magnet did not suspend in plating bath once more with regard to not breaking away from magnet.That is, if in a single day surface magnetic flux density more than 0.25 tesla, then is adsorbed on the magnet, organism-metal combination will become the state that always is captured, and consequently, will prevent the absorption on workpiece.
Description of drawings
Fig. 1 is the stereographic map of plating tool.
Fig. 2 is the front view that makes the state of carriage (tray) setting.
Fig. 3 is the stereographic map of carriage.
Fig. 4 is the exploded perspective view of carriage.
Fig. 5 A, Fig. 5 B are the vertical views of substrate.
Fig. 6 is the enlarged view of cell part.
Fig. 7 A, Fig. 7 B are the sectional views of cell part.
Fig. 8 is the sectional view of the cell part of other modes.
Fig. 9 is the figure that is used to illustrate the user mode of electroplanting device.
Figure 10 A, Figure 10 B are the rotational action of explanation carriage and the figure of workpiece movement.
Figure 11 is the figure that is used to illustrate the workpiece movement in the cell.
Figure 12 A～Figure 12 F is the figure of example of the shape of explanation cell.
Figure 13 is other the stereographic map of mode of expression carriage.
Figure 14 is the stereographic map of another mode of expression carriage.
Figure 15 is the chart (embodiment 1) of the thickness at each position of expression.
Figure 16 is the chart (embodiment 2) of the thickness at each position of expression.
Figure 17 is the stereographic map of the integral body picture of expression plating tool.
Figure 18 is the major portion enlarged view that is used to illustrate base portion.
Figure 19 is the major portion enlarged view that is used to illustrate the support portion.
Figure 20 is the figure that is used to illustrate the user mode of electroplanting device.
Figure 21 is the front view of workpiece at the determining film thickness position of expression plated product.
Figure 22 is the sectional view of workpiece at the determining film thickness position of expression plated product.
Figure 23 is the chart of thickness at each position of expression embodiment.
Figure 24 is the chart of thickness at each position of expression comparative example.
Figure 25 is the schema of the basic technology example of expression solution and coating method.
Figure 26 is the enlarged view of the pin hole cut-away section of plating.
Figure 27 is the figure of the results of elemental analyses of expression foreign matter.
Figure 28 is the figure of the summary of expression electroplanting device of the present invention.
Figure 29 is the figure of configuration of the magnet of expression comparative example.
Embodiment
Below with reference to accompanying drawings embodiments of the present invention are described.
Fig. 1 is the stereographic map of summary of the plating tool 100 of expression embodiments of the present invention 1.This plating tool 100 is instruments of electroplating usefulness, about framework 13a, 13b between, have 2 carriage 10a, 10b as the supporter that freely rotates.On this carriage (tray) 10a, 10b, the room as the workpiece 70 that disposes plated body is formed with a plurality of cells 30 respectively.This cell 30 is by the inner-wall surface that is formed at the pass through openings on carriage 10a, the 10b, limited as transversal cathode rays 33a, 33b.And, around each cell 30, be provided with the portion that digs 37 as the plating bath guidance part.
Fig. 2 is a state of seeing plating tool 100 from the front, and what represent here is the state that carriage 10a and 10b near normal ground are erect, and disposes workpiece 70 in each cell 30.
On framework 13a, be equipped with the 1st gear the 21, the 2nd gear the 23, the 3rd gear 25 with the state that is mutually locked.The 2nd gear the 23, the 3rd gear 25 runs through the through hole (not shown) of framework 13a respectively and is connected with carriage 10a, carriage 10b.The 1st gear 21 folder bulkhead frame 13a connect with the CD-ROM drive motor 27 of an opposite side.
Be provided with pillar 15 on the top of plating tool 100, can grip that this part moves or the dipping in plating bath.The face side of plating tool 100 and rear side in addition, also are provided with peristome 19 by opening in the bottom, under the state in impregnated in electroplate liquid, plating bath enters in the cell 30 at an easy rate.
The left and right sides framework 13a of plating tool 100, the top of 13b, 4 positions are provided with the extension portion 17 that is made of conductive materials such as metals in front and back, under the state in impregnated in electroplate liquid, can be with on the club that should extension portion 17 be suspended in across coating bath 50 (with reference to Fig. 9).
In addition, the central part of gear 23 (gear 25) can connect not shown distribution here, thereby can be electrically connected to axle 34 (with reference to Fig. 3) of carriage 10.
Below, with reference to Fig. 3～Fig. 8, the details of carriage 10 (10a, 10b) is described.Fig. 3 is the stereographic map of carriage 10, and Fig. 4 is the exploded perspective view with figure.In addition, Fig. 5 A, Fig. 5 B are the substrate 11a that constitute to overlap the carriage 10 of structure, the vertical view of 11b, present the outside (surface structure) of carriage 10 in Fig. 5 A, in Fig. 5 B, present the inboard (face of facing mutually) of the carriage 10 that has overlapped.And the substrate 11b shown in Fig. 5 B is that substrate 11a and substrate 11b are identical construction basically with the upturned state in the inside of the substrate 11a shown in Fig. 5 A.
On the carriage 10 of present embodiment, be formed with two row cells 30 as the peristome that has connected, whenever show 7.Cell 30 as described later shown in, no matter which turned position carriage 10 moves to, and also still form to connect the shape that the line of a settling position and another settling position can not overlap with vertical direction.
In addition, near the both ends of the pass through openings of the entrance and exit that is equivalent to cell 30,, be formed with the outstanding containment wall 39 that forms according to the mode of dwindling opening.This containment wall 39 has the effect of partly covering workpiece 70 in workpiece 70 being disposed at by the inner-wall surface of cell 30, space that cathode rays 33 marked and carry out under the situation of plating.
Shown in Fig. 5 A, in the present embodiment, in each opening 12, be provided with a pair of containment wall 39, make it outstanding to opening from opposed facing two edge portions (above-below direction of Fig. 5 A of opening 12, the paper of Fig. 5 B) of opening 12.From with can seeing the figure, the opening 12 of substrate 11a is dwindled in the face of the containment wall 39 of turnover mutually by the both sides from opening edge portion.When carriage 10 is handled at plating, because with axle 34 (with reference to Fig. 3 and Fig. 4) is that rotate at the center, therefore containment wall 39 is located in described two edge portions that face mutually, thereby be under the state of settling position (aftermentioned) at the workpiece 70 that in cell 30, moves because of rotation, can cover the bottom of workpiece 70.Like this, just can be with the end face portion of cyclic workpiece 70 and the thickness homogenization in bight.And in Fig. 5 B, the containment wall 39 of substrate 11b is shown in the inside of opening 12.
Around each cell 30,, be provided with the lower slightly and portion that digs 37 (surface of substrate 11b is also identical) that forms in surface (being carriage 10 surfaces) than substrate 11a to each cell.This digs portion 37 and promotes the part that the plating bath guidance part of the inflow of plating bath in cell 10 plays a role as the rotation because of carriage 10.In addition, dig portion 37 owing to be located on each opening 12, therefore according to making the rotation that is accompanied by carriage 10, the liquid measure of the plating bath of inflow cell 30 is for all impartial mode effect of each cell 30.
In the present embodiment, dig portion 37 and constitute by opening edge portion being made than substrate 11a, the lower end difference in 11b surface.Utilize this inflow promoter action that digs portion 37, under the state that the port area of cell 30 is dwindled by being provided with containment wall 39, can guarantee the influx of plating bath, in this particularly advantageous plating bath.
In addition, dig the degree of depth or the area of portion 37 by adjustment, also having can be to the effect of each room control plating bath influx.For example, when because the major causes such as size, plating bath mobile flow velocity or direction of the size of the configuration of the carriage 10 of cell 30, carriage 10 or shape, coating bath 50, when on the plating bath influx of 30 of cells, creating a difference, by each cell 30 is adjusted the degree of depth, size, the shape that digs portion 37, just can make the influx homogenization of the plating bath of each cell 30, in addition, on the contrary can also be wittingly on the influx of the plating bath of each cell 30, keep difference.And as the structure of plating bath guidance part, except end difference, the taper configurations described later as the present embodiment, the edge portion that can also enumerate towards cell 30 is formed at substrate 11a, the lip-deep groove of 11b etc.
On the two sides of carriage 10,, be equipped with 2 cathode rays 33 on each single face to stride the state of whole cells 30 of being located at same column.That is, on the peristome of each cell 30, be crossed with 1 (totally 2 of both sides) cathode rays 33 on each is one-sided.Cathode rays 33 for example is made of conductive materials such as stainless steel, iron, copper, titanium, carbon, engages to have similarly by what conductive material formed on two ends fixedly to have 31a, a 31b or fixedly have 32a, a 32b.
Cathode rays 33 is at the peristome two ends of each cell 30, and promptly exposed on (still, when carriage 10 counter-rotatings, they will be by alternately) napex of peristome and bottom, contacts and has an effect that makes it to switch on the workpiece 70 as plated body in being disposed at cell 30.In addition, when carriage 10 is rotated, workpiece 70 floats in cell 30, the cathode rays 33 that breaks away from downside, but, by on the two sides, setting cathode rays 33, even under the state of come-up, also can be because of contact the effect of the switch-on regime that can guarantee workpiece 70 with the cathode rays 33 of upside.Though the bar number of cathode rays 33 can be each one-sided setting more than 2 of cell 30 in the scope that can not counteract plating, when considering the reduction of the plating efficient that causes to separating out of cathode rays 33 by metal, be preferably in and one-sidedly be provided with 1.And for cathode rays 33, preferably insulation processing is implemented at the position beyond the necessary part of energising of subtend workpiece 70.
And cathode rays 33 is not limited to configured in parallel, for example also can be configured to reticulation.In addition, cathode rays 33 is had as the function that falls anti-locking mechanism that falls that prevents workpiece 70.When workpiece 70 was fallen in the electroplate liquid, metal will be from workpiece 70 strippings, thereby can produce detrimentally affect to plating performance, still, utilized and fell anti-locking mechanism, just can prevent this type of situation.
As previously mentioned, though cathode rays 33 contacts with workpiece 70 and has the function of switching on,, for example on the inwall of cell 30, then do not need cathode rays 33 if with the position of cathode arrangement at other.In addition, when only during as purpose, also can not use cathode rays 33, and to dispose plastic fiber or net etc. in the both sides of carriage 10 as the function that falls anti-locking mechanism.
Fixedly have 31a, 31b have respectively the axle 34.This axle 34 plays a role as rotation axis, can utilize not shown combining mechanism to combine with the 2nd gear 23 or the 3rd gear 25.Axle 34 with have electroconductibility fixedly to have 31a, a 31b integrally formed, thereby can be by the central part of the 2nd gear 23 or the 3rd gear 25 and be connected with not shown wired electric.In addition, fixedly have 32a, 32b except having axle 34, be and fixedly have the roughly the same formation of 31a, 31b.
As shown in Figure 4, fixedly have 31a, 31b (32a, 32b) by metal system bolt etc., be fixed on the substrate 11a (11b) that constitutes carriage 10 by threaded hole 36 and the threaded hole 38 that is formed on the tab 35.In addition, fixedly have the 31a and a 32a of fixedly having and fixedly have 31b and a 32b quilt of fixedly having and installed according to the mode that sandwiches two resin board 11a, 11b.That is, among Fig. 4, the 31a of fixedly having of upside is fixedly had the 32a quilt according to waiting the mode of guaranteeing status of electrically connecting to constitute by the metal system bolt of the threaded hole 38 that runs through tab 35 up and down with next.Like this just can be when the fixedly tool with electroconductibility that constitutes carriage 10 being implemented be used to suppress the meaningless covering of separating out of metal and handling, carry out energising by metal system bolt etc.
As previously mentioned, carriage 10 is structures that 2 plate base 11a, 11b are coincided together.2 plate base 11a of cathode rays 33, the structure that 11b fits together will be on single face, set by adopting like this, just carriage 10 can be made simply.
On substrate 11a, 11b, be formed with the opening 12 that becomes cell 30 with the state Cheng Liezhuan that overlaps.Constitute substrate 11a, the 11b of carriage 10 owing to form, therefore except the effect of supporting workpiece 70, also bring into play shielding effect by non-conductive materials such as for example synthetic resins.In addition, carriage 10 forms the structure of also having guaranteed opening 12 area in addition fully.Will when rotating, carriage 10 have the effect of stirring plating bath like this.On the single face of substrate 11a, 11b, be respectively equipped with the groove 16 that to bury cathode rays 33 underground.
The detailed structure of expression cell 30 among Fig. 6, Fig. 7 A and Fig. 7 B.Be near the major portion vertical view the cell 30 of carriage 10 with figure, Fig. 7 A be the VIIa-VIIa of Fig. 6 to sectional view, Fig. 7 B is the enlarged view in the zone that surrounds of the single-point line by Fig. 7 A.Here, be the state that in cell 30, has disposed cyclic workpiece 70.
Shown in Fig. 7 A, Fig. 7 B, near the cell 30 of carriage 10 cross-sectional configuration forms following formation, promptly, form the portion 37,37 that digs from the two sides, the outside of the substrate 11a, the 11b that overlap, be equipped with the containment wall 39,39,39,39 of 4 positions towards the opening of cell 30, also be equipped with a pair of cathode rays 33a, the 33b that is embedded among substrate 11a, the 11b in addition.
Shown in Fig. 6, Fig. 7 A and Fig. 7 B, in order to obtain sufficient screening effect, in the present embodiment, compare with the width L1 that has formed cyclic workpiece 70, make the total thickness L of dielectric substrate 11a, 11b bigger.For example, when making L1=L, cover just insufficiently, on the particularly periphery of workpiece 70, will form thicker film, and by making L1＜L, screening effect is just more reliable, consequently, can obtain the thickness of homogeneous.
In addition, cathode rays 33a, 33b are set by the mode according to nip substrate 11a, 11b.
That is, cathode rays 33a, 33b are installed according to the mode that is embedded in the groove 16 (with reference to Fig. 4) that is formed on substrate 11a and the 11b, thereby limit cell 30.So the distance L 2 between the 33a of cathode rays up and down, the 33b that faces mutually will be less than the total thickness L of substrate 11a, 11b.Consequently, because the workpiece 70 that is supported by cathode rays 33a, 33b is hidden in the opening wall of substrate 11a, 11b, therefore can obtain sufficient screening effect.In addition, by burying cathode rays 33a, 33b in the groove on being formed at substrate 11a and 11b 16 underground, cathode rays 33a, 33b can be firmly fixed, thereby can prevent bending or distortion, skew etc.
And shown in Fig. 7 A, cathode rays 33a, 33b are by according to setting from the outstanding slightly to the inside mode of the wall of the cell side of containment wall 39.That is, the distance L between the wall of the inboard of containment wall 39 3 is longer than the distance L between cathode rays 33a, 33b 2.This be because, by not contacting of workpiece 70 and cathode rays 33 can be hindered by crested wall 39, and utilize cathode rays 33a, 33b to limit moving of workpiece 70 in the cell 30, prevent that workpiece 70 from contacting and irremovable situation (tangling) with the top of containment wall 39.
And, in this example, the difference of the width L1 of distance L 2 between two cathode rays 33a, 33b and workpiece 70 is set at about 1mm.If the difference of this L2 and L1 is excessive, then owing to workpiece 70 can irrespectively reverse in cell 30 with the action of carriage 10 or replace in length and breadth, thereby therefore the rotation of a uncontrollable direction preferably adjusts the distance L 2 between cathode rays 33a, the 33b up and down according to the shape of workpiece 70.In addition, the relation for the width L1 of distance L 3 between the wall of the inboard of containment wall 39 and workpiece 70 when on the junction surface of substrate 11a, 11b ladder being arranged, can not tangled in order to make workpiece 70 there, L3 is made as 2 times that are no more than L1.
In addition, in order to bring into play bridging effect, the height h of containment wall 39 preferably guarantees enough height.Specifically, shown in Fig. 7 B, when workpiece 70 is ring-type, make the thickness L4 of the height h (height of the wall of upwards erectting from the inner-wall surface of cell 30) of containment wall 39 greater than workpiece 70 perimembranous.
Fig. 8 represents near the cross-sectional configuration the cell 30 of embodiment 2, is the sectional view of the position identical with Fig. 7 A.Here, made from opening towards one-tenth mortar shape unfolded inclined-plane, the surface of substrate 11a, 11b digging portion 37.Utilize the portion that digs 37 of this kind taper configurations, also can obtain the inflow effect of plating bath in the same manner with end difference (Fig. 6, Fig. 7 A and Fig. 7 B).
Fig. 9 is configured in electroplanting device 110 on the coating bath 50 with plating tool 100.Plating tool 100 is hung on excellent 60a, the 60b in the extension portion 17 of 4 positions, and is impregnated into specific position.As previously mentioned because axle 34 can be connected with external electric via the central part of the 2nd gear 23 or the 3rd gear 25, so by distribution to this central part, will be energized to the cathode rays 33 of carriage 10a, 10b.In addition, set anode 41 by the both sides at plating tool 100, produce electrochemical reaction, the metal ion in the plating bath 50 will be separated out to the surface of the workpiece 70 that contacts with cathode rays 33, forms overlay film.
When using plating tool 100 to carry out plating, utilize CD-ROM drive motor 27 that the 1st gear 21 is rotated with specific speed.The motion of the 1st gear 21 both can be the rotation to single direction, also can be the rotation to both forward and reverse directions, or did not form the swing of rotation.And, when CD-ROM drive motor 27 is not set, also can be by manually carrying out this action.The rotation of the 1st gear 21 is passed to the 2nd gear 23, and the 2nd gear 23 is rotated.Equally, the rotation of the 2nd gear 23 is passed to the 3rd gear 25, and the 3rd gear 25 is rotated.For example, in the 1st gear 21 direction shown in arrow when rotation in Fig. 9,, the 2nd gear the 23, the 3rd gear 25 is respectively along the direction rotation of arrow.
The rotation of the 2nd gear 23 and the 3rd gear 25 directly is passed to carriage 10a, 10b through axle 34, and carriage 10a, 10b promptly rotate (rotation or swing).
The rotation of expression carriage 10 and moving of the workpiece 70 in the cell 30 among Figure 10 A, Figure 10 B.And,,, only illustrate the cell 30 of the one-sided row of carriage 10 here for the convenience that illustrates, simultaneously, cathode rays 33, the diagram that digs portion 37, containment wall 39 etc. are omitted, adopt simple open construction to represent.At first, consider that carriage 10 rotates to the situation of B position along direction shown in the thin arrow the figure from the A position shown in Figure 10 A.Workpiece 70 in the A position, cell 30 are positioned at the position by the end, promptly with the inner-wall surface position contacting of cell 30.Along with carriage 10 rotates to the B position, the workpiece 70 in the cell 30 moves to base end side in cell 30 slightly promptly towards direction shown in the thick arrow.More particularly, on one side with not shown here cathode rays 33 sliding contacts, move on one side.
When carriage 10 rotated to the C position, the workpiece 70 in the cell 30 promptly were positioned at fully the position near base end side, that is, become and the wall state of contact of facing mutually with the wall of the head of cell 30.
When carriage 10 reached D position shown in Figure 10 B, workpiece 70 reversed, and became cathode rays 33 state of contact with the opposite side of cell 30.When carriage 10 rotated to the E position along the thin direction of arrow once more from the D position, 70 of the workpiece of counter-rotating moved to the end side of carriage 10 along direction shown in the thick arrow in cell 30 once more.When carriage 10 rotated again and arrives the F position, workpiece 70 promptly became the inwall state of contact with cell 30, rotated once more soon and returned the state of the A position of Figure 10 A.Like this, utilize the rotation of carriage 10, workpiece 70 moves in cell 30, and simultaneously, when carriage 30 counter-rotatings, workpiece 70 also reverses.And, though the thick arrow of Figure 10 A, Figure 10 B is the direction that moves of the workpiece 70 in the expression cell 30, should moves and cause by gravity.
Figure 11 is the synoptic diagram that moves that is used to illustrate the workpiece 70 of plating tool 100 of the present invention.Here, also suitably describe with reference to Figure 10 A, Figure 10 B.And among Figure 11 A～D, cell 30 presents simple quadrangle (vertical view), and thick arrow is represented the travel direction of workpiece 70, and the arrow of thin circular arc is represented the sense of rotation of workpiece 70.In addition, the line Y that has arrow at two ends that is drawn on the sidepiece of each figure represents to connect the base end part (turn center) of carriage 10 and the line direction of end (following note is sometimes made " Y-axis ") with shortest distance.
At first, among Figure 11 A, workpiece 70 is for being supported on the state of a settling position in the cell 30.At this moment, suppose that cell 30 is positioned at the A position of Figure 10 A.
From the state of Figure 11 A, along with carriage 10 moves to the C position through the B position of Figure 10 A, the workpiece 70 in the cell 30 in cell 30 towards the base end part side shifting of carriage 10.Specifically, on one side with cathode rays 33 (not shown) sliding contact of the bottom that is equipped on cell 30, the thick direction of arrow of edge Figure 11 A moves to the opposed wall of cell 30.In addition, the workpiece 70 of colliding with opposed wall in the cell 30 in the wall rotation, moves along direction shown in the thick arrow shown in Figure 11 B, arrives another settling position [position of Figure 11 C] of this cell 30.
When making carriage 10 rotations again, through D position, the E position of Figure 10 B, when moving to the F position, the counter-rotating up and down of workpiece 70 is moved along direction shown in the thick arrow among Figure 11 C.Specifically, with the electrode sliding contact that is equipped on the bottom in, move to opposed wall of cell 30.Because the rotation of carriage 10, the workpiece 70 of colliding with opposed wall of cell 30 moves along direction shown in the thick arrow among Figure 11 D in the wall rotation, arrives the initial settling position [position of Figure 11 A] of this cell 30.
By carrying out above action repeatedly, workpiece 70 along the discontinuous rotation of single direction, moves in cell 30 simultaneously.Be not limited to make the situation of carriage 10 rotations, under making it, if workpiece 70 similarly can obtain the rotation of single direction because of deadweight mobile angle cell 30 in situation less than 360 ° angle swinging.The rotation of this single direction is the rotation that has the right angle vector with respect to the rotating vector axle of carriage 10.Utilize this rotation, in having the cyclic workpiece 70 of inner peripheral surface 70b, implement the plating of thickness homogeneous in interior periphery.
That is, utilize the rotation of workpiece 70, the periphery 70a of workpiece 70 changes successively with the position that the wall of cell 30 contacts, consequently, because the screening effect of homogeneous, the thickness of the periphery 70a homogeneous that becomes.
In addition, the periphery 70a of workpiece 70 is owing to suitably covered by the wall of cell 30, therefore suppress overlay film and form, the only situation of the plating thickening of periphery 70a can not take place, thereby can improve the film thickness difference that becomes with the inner peripheral surface 70b of the workpiece 70 that is difficult to form plating and dwindle.In addition, by containment wall 39 is set, for end face, periphery bight, interior all bights of cyclic workpiece 70, also can formation and the thickness of periphery or interior Zhou Xiangtong degree, thus can obtain to have the product of very high-precision overlay film.
In addition, because end face and cathode rays 33 contacts site of workpiece 70 can change at short notice along with the rotation of workpiece 70, so can be not bonding with cathode rays 33.Usually, known when workpiece 70 overlay film and during electrode adhesion, will cause damaged (plating is peeled off) of overlay film, and become the iron rust that causes as bad order of decorating plating or metal species plated body and produce reason, but, the present invention can prevent this type of situation, nor can residual any tool mark.
Among Figure 11, though according to making the mode of overlooking to tilt with respect to Y-axis into dimetric cell 30, for example dispose with angle θ, but from seeing the figure, even identical quadrangle, by the angle θ (this means the shape that change cell 30) of change, also can regulate rotation amount with Y-axis.
As shown in figure 11, follow the rotation of carriage 10, the workpiece 70 in the cell 30 moves because of gravity.Utilize and to move, and do not operate, just can make workpiece 70 rotation in a certain direction in cell 30 with the mode that Y-axis [with reference to Figure 11] overlaps according to the mobile route that makes workpiece 70.When considering that carriage 10 has formed the state of erectting in the rotation way, just can easily understand this situation.Carriage 10 is under the state of erectting (the C position of Figure 10 B, F position), and Y-axis overlaps with vertical direction.So, (for example to overlook and be circle or rhombohedral situation etc.) when the line of the settling position in for example connecting cell 30 overlaps with Y-axis, the workpiece 70 in the cell 30 will move with shortest distance near free-falling state lower edge Y-axis.Under the mobile situation of this kind, just can't workpiece 70 be rotated along single direction.Even suppose to have produced rotation, because uncontrollable its sense of rotation, therefore also can not the controls revolution amount.
But, if settling position [position of Figure 11 A] in the cell 20 that connects workpiece 70 and the straight line of another settling position [position of Figure 11 C] are not overlapped with Y-axis (vertical direction), then can make workpiece 70 contact and be rotated on the way mobile with the wall of cell 30.Because this rotation is a certain orientation, so the control of rotation amount also is easy to.And therefore the rotation of workpiece 70 be there is no need to adopt complicated mechanism owing to do not cause by the rotation of carriage 10 and the shape of cell 30.
The shape of cell 30 (overlooking) is not limited to quadrangle.Among Figure 12 A～Figure 12 F, the example of the shape (overlooking) of expression cell 30.Among the figure, Figure 12 A is a parallelogram, and Figure 12 B is trapezoidal, and Figure 12 C is a pentagon, and Figure 12 D is a quadrangle, and Figure 12 E is oval, and Figure 12 F is an endless belt shape, and arrow is represented the travel direction of workpiece 70.The length of arrow is represented the length of miles of relative movement, and dotted line is represented not moving of accompanying rotation.Can see from Figure 12 A～Figure 12 F, utilize the shape of cell 30 can change the rotation amount of workpiece 70.In addition, if the shape of cell 30 is identical, then the rotation of workpiece 70 just always in the same direction.
For workpiece 70 is rotated effectively, shown in example among Figure 11 and Figure 12 A～Figure 12 F, preferably the shape of cell 30 is made with respect to the symmetric shape of the non-line of Y-axis.When being provided with like this, just can easily produce the cell 30 of the shape that connection do not overlap as the position of Figure 11 A of a settling position with as the line of the position of Figure 11 C of another settling position and vertical direction.Promptly, in the spinning movement of carriage 10, owing to be easy to form the structure that workpiece 70 contact with at least one contact site of the wall of cell 30 from a settling position because of gravity to the way that another settling position moves, so just can apply rotation to plated body.Like this, by controlling the shape of the cell 30 that disposes workpiece 70, just can apply required rotation, thereby can form the overlay film of homogeneous workpiece 70.
Used the plating of plating tool 100 of the present invention can be according to implementing with common plating process and condition.If the summary when example utilizes plating tool 100 of the present invention to electroplate then at first, is positioned workpiece 70 in the cell 30, after having carried out as required cleaning, under specific currents, carries out tarnish plating or semi-gloss plating or gloss and electroplate.The plating thing by carrying out drying, just can obtain final plated product after cleaning.
As the workpiece 70 of plated body, for example be preferably the shape that discoideus, cylindric, ring-type, ball etc. rotate along interior Zhou Fangxiang easily cell 30 in.Particularly, in plating, the inner peripheral surface 70b of, ring-type cylindric etc. for having, and utilize the workpiece 70 that has used the plating of instrument in the past just to be easy to form the shape of inhomogenous thickness in interior periphery, very effective.
As the material of plated body, though metal, nonmetal all can, be difficult to implement the material of accurate plating for metal and nonmetallic mixture or the metal etc. that has an emptying aperture with common instrument, also very effective.As this type of material, for example can enumerate mixture, casting alloy of sintered alloy, resin and powder metal etc., more particularly, for example can enumerate sintered magnet, binding magnet, casting magnet etc.
As described magnet raw material,, be not particularly limited though for example can enumerate following [1]～[6].
[1] will be based on the transition metal of R (wherein R is at least a kind that contains in the middle of the rare earth element of Y), Co material as basal component.
[2] will be based on the transition metal (TM) of R (wherein R is at least a kind that contains in the middle of the rare earth element of Y), Fe and B material as basal component.
[3] will based on the transition metal (TM) of R (wherein R is at least a kind that contains in the middle of the rare earth element of Y), Fe and based on element between the lattice of N as the material of basal component.
[4] will be with transition metal (TM) such as R (wherein R is at least a kind that contains in the middle of the rare earth element of Y), Fe as basal component and have the soft magnetism material of the complex tissue of mutually adjacent with hard magnetic (comprising that also folder is every the mutually adjacent situation of crystal boundary) existence (especially, have be called as the nano composite material tissue) mutually.
[5] with at least 2 kinds of blended materials in the middle of the material of the composition of described [1]～[4].
[6] with at least a kind in the middle of the material of the composition of described [1]～[4] and ferrite powder (SrO6Fe for example
2Sr-ferrites such as O3 etc.) blended material.
In addition, as the employed binding resin of binding magnet (caking agent), can enumerate thermoplastic resin, thermosetting resin etc.As thermoplastic resin, for example can enumerate the polymeric amide that is commonly referred to as nylon, thermoplastic polyimide, polyethylene terephthalate etc., can use a kind in the middle of them or be mixed with two or more.
On the other hand,, for example can enumerate Resins, epoxy, resol, polyimide resin etc., can use a kind in the middle of them or be mixed with two or more as thermosetting resin.
[embodiment 1]
The present invention will be described in more detail to utilize embodiment, experimental example below, and still, the present invention is not limited by they.
Utilize plating tool of the present invention 100 and plating tool relatively, carry out plating respectively, the thickness and the outward appearance of the plated product of gained compared.The condition of plating is as follows.
＜plated body 1 〉
For plated body, used the cyclic n nitroso compound d-Fe-B class binding magnet of external diameter 9.4mm, internal diameter 7mm, high 1.2mm.
＜plating condition 1 〉
(1) plating tool of the present invention:
Plated body is positioned in the plating tool shown in Figure 1, after the cleaning, with 2A/dm
260 minutes plating have been carried out.The plated product of gained carries out drying after having carried out cleanings such as the cleaning of ultrasonic wave water, hot water cleaning.
Per 1 batch processing number is made as 28, and the speed of rotation of the carriage 10 in the plating adopts 3～4rpm.
(2) compare plating tool:
Dig the portion 37 except not being provided with, to use the instrument of the formation identical with plating tool of the present invention 100, with described identical condition under carried out plating.
＜measure and result 1
For the plated product of gained, measured the thickness in periphery, inner peripheral surface, end face A, end face B, periphery bight, interior all bights.Its result is illustrated among Figure 15.As seen from Figure 15, use plating tool 100 of the present invention to carry out the plated product of plating, the film thickness difference minimum in periphery, interior week, end face A, end face B, periphery bight, interior all bights, thereby be homogeneous.In addition, owing to be accompanied by the rotation of carriage 10, workpiece 70 rotates in cell 30, therefore also not residual tool mark.In contrast, relatively better though the thickness in periphery and interior week is a same degree for the situation of plating tool relatively, what produce on the thickness in all bights in they and end face, periphery bight reach is certain poor.
[embodiment 2]
In addition, the present invention will be described in more detail to utilize embodiment, experimental example, and still, the present invention is not limited by they.
Utilize plating tool of the present invention 100 and plating tool relatively, carry out plating respectively, the thickness and the outward appearance of the plated product of gained compared.The condition of plating is as follows.
＜plated body 2 〉
Plated body has used the ring-type rare-earth bond magnet of external diameter 19mm, internal diameter 17mm, high 3.6mm.In this magnet, mixing is ferromagnetic powder (the MQP-B powder of MQI corporate system), Resins, epoxy, a spot of hydrazine class antioxidant that R-TM-B class alloy constitutes by alloy composition, they were mixed 30 minutes at normal temperatures, made binding magnet composition (compound).At this moment, the cooperation ratio (part by weight) of ferromagnetic powder, Resins, epoxy, hydrazine class antioxidant is respectively 95wt%, 4wt%, 1wt%.
Then, the weighing said composition also is filled in the mould of pressing unit, in no magnetic field, after normal temperature, pressure 1370MPa compression molding, under 170 ℃ Resins, epoxy is heating and curing, and has obtained binding magnet cylindraceous.This binding magnet has been implemented the milled processed of its short transverse.Thereafter, utilizing the cylinder polishing that binding magnet is ground to each rib becomes R0.2, with it as magnet main body.
＜plating condition 2 〉
(1) plating tool of the present invention:
Plated body is positioned in the plating tool shown in Figure 1, after the cleaning, uses 50 ℃ matt watt to bathe, with 2A/dm
2Carried out 30 minutes matt plating, bathed with 50 ℃ gloss watt then, with 2A/dm
2Having carried out 20 minutes gloss electroplates.The plated product of gained carries out drying after having carried out cleanings such as the cleaning of ultrasonic wave water, hot water cleaning.
Per 1 batch processing number is made as 28, and the speed of rotation of the carriage 10 in the plating adopts 3～4rpm.
(2) compare plating tool 1:
Except containment wall 39 not being set and digging portion 37, and the cathode rays 33 of transversal cell 30 is made as beyond one-sided 2, uses the instrument of the formation identical with plating tool of the present invention 100, with described identical condition under carried out plating.
(3) compare plating tool 2 (tool drum):
Used tool drum (instrument of known formation).Plated body is positioned in the tool drum, after the cleaning, uses 50 ℃ matt watt to bathe, with 1A/dm
2Carried out 100 minutes matt plating, bathed with 50 ℃ gloss watt then, with 1A/dm
2Having carried out 6.0 minutes gloss electroplates.The plated product of gained carries out drying after having carried out cleanings such as the cleaning of ultrasonic wave water, hot water cleaning.
The processing number of per 1 batch (cylinder) is made as 30, simultaneously, in cylinder, has dropped into the nickel ball 200ml of diameter 5mm.In addition, the speed of rotation of the carriage in the plating 10 adopts 3～4rpm.
＜measure and result 2
For the plated product of gained, indistinguishably extract 4 samples out, measured the thickness in periphery, inner peripheral surface, end face A, end face B, periphery bight, interior all bights.Its result is illustrated among table 1 and Figure 16.
Table 1
| Plating tool | Thickness (unit: μ m) | Precipitation efficiency * (％) | |||||
| Periphery | Interior week | End face A | End face B | The periphery bight | Interior all bights | ||
| Plating tool of the present invention | 23.8 | 21.3 | 26.3 | 25.0 | 28.0 | 27.5 | 69.7 |
| Compare | 23.5 | 22.3 | 34.3 | 39.0 | 38.0 | 35.8 | 53.5 |
| Compare plating tool 2 | 48.8 | 17.5 | 58.8 | 63.3 | 63.8 | 42.8 | 21.0 |
*According to workpiece the amount of separating out/all the amount of separating out (electrode, instrument, workpiece) is calculated.
From table 1 and Figure 16, can see, use plating tool 100 of the present invention to carry out the plated product of plating, the film thickness difference minimum in periphery, interior week, end face A, end face B, periphery bight, interior all bights, thereby be uniform.In addition, owing to be accompanied by the rotation of carriage 10, workpiece 70 rotates in cell 30, therefore also not residual tool mark.In addition, for the plating precipitation efficiency, also demonstrated 69.7% good like this value.
In contrast, for utilizing the relatively plating of plating tool 2 (tool drum), the inequality of thickness is bigger, thereby can't make the homogenizations such as thickness in inner peripheral surface and periphery, periphery bight and interior all bights.In addition, the plating precipitation efficiency is 21.0%, and about 8 one-tenth dielectric drums to energising usefulness are separated out.
In addition, relatively under the situation of plating tool 1, relatively better though the thickness in periphery and interior week is a same degree, what produce on the thickness in all bights in they and end face, periphery bight reach is certain poor.In addition, precipitation efficiency is 53.5%.This is considered to because compare with instrument of the present invention, and the bar number of electrode (cathode rays 33) is more.
And, for supplementary anode instrument (opening the identical formation of 2001-73198 communique), carried out and described identical experiment with the spy.In this instrument, because the supplementary anode that has nickel system in the central authorities of the circular support tool of double as negative electrode, so workpiece is located at 3 fins of inner peripheral surface of circular support tool with 3 supports in its periphery.Anodic configuration in the plating bath is identical with Fig. 3.The plating condition is, plated body is positioned in the plating tool, after cleaning, uses 50 ℃ matt watt bath, with 2A/dm
2Carried out 60 minutes matt plating, bathed with 50 ℃ gloss watt then, with 2A/dm
2Having carried out 20 minutes gloss electroplates.The plated product of gained carries out drying after having carried out cleanings such as the cleaning of ultrasonic wave water, hot water cleaning.Per 1 batch processing number is made as 16, remains static in the plating.And, owing at the residual tool mark that stays with contacting of fin of periphery, therefore in the mensuration of plating thickness, avoid this part and measure.Consequently, though the inequality of thickness is not too big, can see foreign matter adhering on plated product.The nickel that this foreign matter is considered to use in the supplementary anode breaks away from back formation.In addition, as previously mentioned, tool mark arranged in that periphery is residual.
And, though to using insoluble anode material (SUS, titanium-platinum, carbon etc.) also to test, can't obtain the anode effect substantially, the film thickness difference of periphery in can't improving as the situation of other supplementary anodes.
Though more than with various embodiments the present invention is narrated, the present invention is not limited to described embodiment, in the described scope of invention of the scope of claim, also goes for other embodiment.
For example, though the plating tool 100 that (Fig. 1) use to electroplate usefulness in described embodiment 1 is illustrated, on the carriage 10 that freely rotates in the room (cell 30) of formation independent individual configuration the structure of workpiece 70 also can be used for the situation of electroless plating.Under this situation, can replace cathode rays 33,, set synthetic resins line etc. as transversal.
In addition, carriage 10 is not limited to the illustrated formation of Fig. 1, for example also can be in the such formation of the carriage shown in Figure 13 111 as embodiment 3.This carriage 111 does not have containment wall, as the plating bath guidance part, is provided with the portion that digs 120 to the cone-shaped of carriage 111 unfolded surfaces from opening edge portion.Carriage 111 is the parts that use as the instrument of electroplating usefulness, form shorter along its gyration vector direction of principal axis size, tabular along its radius of gyration direction longer dimension.In addition, also the structure of conduct with the area of the wall portion 80 of the contact surface of plating bath guaranteed in formation fully.Utilize this kind shape, can guarantee the agitating function of plating bath fully.In addition, can promote greatly plating bath from the wall portion 80 that widened area to the inflow that digs portion 120.
Figure 14 is the stereographic map of summary of the carriage 112 of expression embodiment 4.This carriage 112 is the parts that can be used for electroless plating, does not have containment wall, does not also set electrode.Workpiece 70 (not shown) can be provided with and suitable fall anti-locking mechanism (line, net, fin, tab etc.) and be disposed in the cell 30.Here, by disposing 2 tabular components or 4 tabular components, improve agitating function according to being seen as criss-cross mode from the side.In this carriage 112, wall portion 80 has also guaranteed sufficient area.In addition, as the plating bath guidance part, have by being provided with and make the opening edge portion stagewise end difference lower constitute the portion of digging 121 than carriage 112 surfaces.Like this, just can promote widely plating bath from the wall portion 80 that widened area to the inflow that digs portion 121.
In addition,, can increase cell 30 by according to seeing that from the side being criss-cross mode disposes tabular component, thus can a plurality of workpiece 70 of primary treatment.
And, though be illustrated with the example that does not set electrode among Figure 14, preventing the cathode rays (symbol 33) that falls by on carriage 112, setting double as, also can be used for electroplating.
In addition, among Figure 14,, also can improve agitating function in the same manner though,, for example adopt 3 (side is seen as the Y font) tabular components according to seeing that from the side being criss-cross mode has disposed tabular component in order to improve agitating function.In addition, as long as in the scope that can install in design, tabular component can also be made as the formation more than 5, also can expect sufficient mixing effect for this formation.
Figure 17 is the stereographic map of summary of the plating tool 200 of expression embodiments of the present invention 5.This plating tool 200 is the plating tools that are suitable for enforcement plating such as ring-type binding magnets, on the axle 210 of striding the rotation axis of being located between left and right sides framework 13a, the 13b, as base portion, is provided with 2 rotating disk 211a, 211b here.On each rotating disk 211a, 211b, respectively be provided with 8 support portions 231 that are used to hang as the workpiece 270 of plated body.And here, expression hangs over state on each support portion 231 with workpiece 270.
On framework 13a, be equipped with the 1st gear 221 and the 2nd gear 223 with the state that is mutually locked.The through hole (not shown) that the 2nd gear 223 passes framework 13a is connected with axle 210.The 1st gear 221 folder bulkhead frame 13a connect with the CD-ROM drive motor (not shown) of an opposite side.
Be provided with grip part (pillar) 15 on the top of plating tool 200, can grip that this part moves or the dipping in plating bath.The face side of plating tool 200 and rear side are opened wide, and in addition, also are provided with peristome 219 in the bottom, are formed on the structure that plating bath circulates easily under the state that impregnated in the plating bath.
Top at the left and right sides of plating tool 200 framework 13a, 13b, on 4 positions, front and back, be provided with the extension portion 217 that constitutes by conductive materials such as metals, under the state in impregnated in plating bath, just can be with on the club that should extension portion 217 be suspended on across coating bath 250 (with reference to Figure 20).
In addition, the central part of gear 223 can connect not shown distribution here, can be electrically connected to the necking part 235 of supporting pin 234 by axle 210 that is made of metal saw lumber matter such as SUS and rotating disk 11.Expose the metallic surface of the necking part 235 of supporting pin 234, by with this part supporting workpiece 270, makes workpiece 270 energisings.
Necking part 235 contacts with the inner peripheral surface of workpiece 270 as constituting along the smooth side face of the axis direction of supporting pin 234, plays a role according to the mode that it is stably kept.The width of necking part 235 (L1) can be as described later shown in, set according to the width of workpiece 270.
Tapering 236a, 236b by with the orthogonal direction of the axis direction of supporting pin 234 be benchmark, the face that tilts with angle θ forms.Here, the tiltangle of taper can be set aptly according to the size and the perimembranous wall thickness of workpiece 270, for example can be set at 30 °～85 °, preferably is set at 45 °～75 °.
And in the time will only utilizing the conical surface (V-shaped valley) that workpiece 270 is stably kept, the interior week of workpiece 270 might be along the groove contact of tilting, integral inclination, in addition, workpiece 270 also may excessively enter in the groove, its end face (with reference to Figure 22) becomes shade, thereby overlay film forms insufficient.At this moment, when the reduced width with V-shaped valley extremely can not make end face become shade, workpiece 270 just broke away from easily.
In addition, on the contrary, when necking part 235 only is set, when tapering 236a, 236b ground setting end difference (the angle θ that is Figure 19 is 0) are not set, as described later shown in the comparative example,, become under the situation of wall state of contact of its end and certain end difference of the left and right sides in the position of workpiece 270 deflection, the formation of plating that might this position is insufficient, thereby causes the thickness inequality.In addition, necking part 235 and tapering 236a, 236b be not provided with, supporting pin 234 is formed along axis direction under the situation of smooth formation, the position of workpiece 270 also can be unstable, when when rotating disk 11 sides or plectane 233 lateral deviations are oblique, can produce same problem.So,, tapering 236a, 236b are set in both sides preferably according to the mode that necking part 235 is clipped in the middle.
At the head end of supporting pin 234,236b is adjacent with the tapering, is provided with the plectane 233 as the anti-locking mechanism that comes off.When even the workpiece 270 that tangles at supported pin 234 revolves round the sun in plating bath, because of liquid stream or liquid resistance etc. under the situation of necking part 235 come-ups, this plectane 233 also can make it can not break away from supporting pin 234.When workpiece 270 is fallen in the plating bath, though metal stripping from workpiece 270 is arranged, plating performance is caused dysgenic situation,, utilize the anti-locking mechanism that comes off can prevent the generation of this type of situation reliably.
In addition, though plectane 233 and supporting pin 234 also can form one, for example also can adopt materials such as synthetic resins can form plectane 233 discretely.And the diameter by making plectane 233 even plectane 233 and supporting pin 234 are being made under the situation of one, also can easily carry out the dismounting of workpiece 270 less than the internal diameter of workpiece 270.
As the anti-locking mechanism that comes off, be not limited to plectane 233, for example also can wait and prevent coming off of workpiece 270 by the cephalic par of supporting pin 234 being made the T font.But, under the situation of making plectane 233, owing to have slick periphery, therefore can obtain following advantage, that is, and in any one moment that the revolution of supporting pin 2344 is moved, can support the side face of the workpiece 270 that is about to come off in the same manner, thereby prevent to come off.
In the plating tool 200 of present embodiment 5, utilize the rotation of the rotating disk 11 that freely rotates with axle 210, can make support portion 231 is to revolve round the sun in the center with axle 210.At this moment, be located at the support portion 231 of last each 8 position of rotating disk 211a, 211b because the mode that overlaps according to revolution orbit is arranged in circle, therefore just can be with condition approximate equality ground distribution such as the electric field that in plating bath, is subjected to, fluid resistances.In addition, be accompanied by the revolution of support portion 231, the workpiece 270 that is hung on the supporting pin 234 that constitutes support portion 231 also can be rotated in the contact position of slight modification inner circumferential surface, forms the plating of homogeneous at Zhou Fangxiang, and does not stay tool mark.
In addition, owing to support portion 231 is located on last each 8 position of rotating disk 211a, 211b, therefore can a plurality of workpiece 270 of primary treatment.So, by workpiece 270 being hung on each support portion 231, can be in the control of carrying out the plating thickness, the processing of corresponding a greater number.
In addition, utilize the revolution of a plurality of support portions 231, also have the effect of stirring plating bath 250, handle thereby can carry out plating effectively.
Like this, in the plating tool 200 of present embodiment 5, owing to can switching on workpiece 270 is fixing, so the location of workpiece 270 and to take off operation all very easy, efficient is good.And, by utilizing necking part 235 and stably keeping workpiece 270, just can guarantee energising property according to tapering 236a, 236b that the mode that it is clipped in the middle forms, can also reduce mobile (the departing from) of the workpiece 270 in the plating bath simultaneously.In addition, since adopted and the wall of the wall of rotating disk 11 or plectane 233 between folder every the formation of tapering 236a, 236b, therefore the end face of workpiece 270 is difficult to become the shade of two walls, thereby can not produce the difference or the insufficient problem of thickness of the thickness of both ends of the surface.
In above formation, on the metal beyond necessary necking part 235 and tapering 236a, the 236b to the energising of workpiece 270, preferably implement insulation processing as far as possible.
Figure 20 is the electroplanting device 310 that has disposed plating tool 200 in coating bath 250.Plating tool 200 is suspended on excellent 260a, the 260b in 4 extension portions 217, and impregnated specific position to plating bath 251.As previously mentioned, axle 210 be owing to can be connected with the cathodic electricity of outside via the central part of the 2nd gear 223, thus by distribution to this central part, just can be energized to the necking part 235 of support portion 231.In addition, set anode 241 by the both sides at plating tool 200, promptly produce electrochemical reaction, the metal ion in the plating bath 250 is separated out to the surface of the workpiece 270 that contacts with necking part 235, forms overlay film.
When using plating tool 200 to carry out plating, utilize CD-ROM drive motor (not shown) that the 1st gear 221 is rotated with specific speed.The motion of the 1st gear 211 both can be the rotation to single direction, also can be the rotation to both forward and reverse directions, or did not form the swing of rotation.And, when CD-ROM drive motor is not set, also can be by manually carrying out this action.The rotation of the 1st gear 221 is passed to the 2nd gear 223, and the 2nd gear 223 is rotated along direction shown in the arrow.The rotation of the 2nd gear 223 directly is passed to rotating disk 211a, 211b through axle 210, makes each support portion 231 begin revolution, and, the inner peripheral surface one side and necking part 235 sliding contacts of workpiece 270, on one side rotation or swing.
Used the plating of plating tool 200 of the present invention to implement according to common plating process and condition.Summary when utilizing plating tool 200 of the present invention to electroplate is, for example workpiece 270 is hung on the supporting pin 234, after having carried out as required cleaning, under specific currents, carries out that tarnish electroplated or semi-gloss is electroplated or the gloss plating.The plating thing by carrying out drying, just can obtain the finished product after cleaning.
As the workpiece 270 as plated body, the object that for example can hang on the supporting pin 234 just becomes object.Particularly in plating, be easy to inhomogenous cyclic workpiece 2,700 minutes effectively for thickness in the plating that uses instrument in the past.
As the material of plated body, though metal, nonmetal all can, be difficult to implement the material of accurate plating for metal and nonmetallic mixture or the metal etc. that has an emptying aperture with common instrument, also very effective.As this type of material, for example can enumerate mixture, casting alloy of sintered alloy, resin and powder metal etc., more particularly, for example can enumerate sintered magnet, binding magnet, casting magnet etc.
As described magnet raw material,, be not particularly limited in them though for example can enumerate following [1]～[6].
[1] will (wherein R be at least a kind that contains in the middle of the rare earth element of Y with R.Below identical.), Co is the main transition metal material as basal component.
[2] will be based on the transition metal (TM) of R, Fe and B material as basal component.
[3] will based on the transition metal (TM) of R, Fe and based on element between the lattice of N as the material of basal component.
[4] with transition metal such as R, Fe (TM) as basal component and have the mutually complex tissue of mutually adjacent with hard magnetic (comprising that also folder is every the mutually adjacent situation of crystal boundary) existence (especially, have be called as nano composite material tissue) material of soft magnetism.
[5] with at least 2 kinds of blended materials in the middle of the material of the composition of described [1]～[4].
[6] with at least a kind in the middle of the material of the composition of described [1]～[4] and ferrite powder (SrO6Fe for example
2O
3On Sr-ferrite etc.) the blended material.
In addition, as the employed binding resin of binding magnet (caking agent), can enumerate thermoplastic resin, thermosetting resin etc.As thermoplastic resin, for example can enumerate the polymeric amide that is commonly referred to as nylon, thermoplastic polyimide, polyethylene terephthalate etc., can use a kind in the middle of them or be mixed with two or more.
On the other hand,, for example can enumerate Resins, epoxy, resol, polyimide resin etc., can use a kind in the middle of them or be mixed with two or more as thermosetting resin.
Though below will enumerate embodiment 3 the present invention is described in more detail, the present invention is not subjected to its any qualification.
Utilize plating tool of the present invention 200 and plating tool relatively, carry out plating respectively, the thickness and the outward appearance of the plated product of gained compared.The condition of plating is as follows.
＜plating tool 〉
As plating tool of the present invention, used instrument shown in Figure 17.Plating tool has as a comparison used except do not utilize vertical end difference to form the necking part 235 on the supporting pin 234 tapering 236a, 236b being set, with the instrument of plating tool 200 identical formations of the present invention.
＜plated body 〉
Plated body has used ring-type rare-earth bond magnet.In this magnet, mixing is ferromagnetic powder (the MQP-B powder of MQI corporate system), Resins, epoxy, a spot of hydrazine class antioxidant that R-TM-B class alloy constitutes by alloy composition, they were mixed 30 minutes at normal temperatures, made binding magnet composition (compound).At this moment, the cooperation ratio (part by weight) of ferromagnetic powder, Resins, epoxy, hydrazine class antioxidant is respectively 95wt%, 4wt%, 1wt%.
Then, the weighing said composition also is filled in the mould of pressing unit, in no magnetic field, after normal temperature, pressure 1370MPa compression molding, under 170 ℃ Resins, epoxy is heating and curing, and has obtained binding magnet cylindraceous.This binding magnet has been implemented the milled processed of its short transverse.Thereafter, utilizing the cylinder polishing that binding magnet is ground to each rib becomes R0.2, with it as magnet main body.
＜plating condition 〉
Plated body is positioned in the plating tool, after cleaning, uses 50 ℃ matt watt to bathe, with 2A/dm
2Carried out 30 minutes matt plating, bathed with 50 ℃ gloss watt then, with 2A/dm
2Having carried out 20 minutes gloss electroplates.The plated product of gained carries out drying after having carried out cleanings such as the cleaning of ultrasonic wave water, hot water cleaning.And, per 1 batch processing number is made as 16.
＜measure and the result
Plated product for gained, indistinguishably extract sample out, for the measuring point of 12 positions from 0 ° to 33 ° shown in Figure 21, measured the thickness of A end face 270a, B end face 270b, periphery 270c and the inner peripheral surface 270d of workpiece shown in Figure 22 270 (ring-type plated product).Its result is illustrated among table 2 and Figure 23 (result of plating tool of the present invention) and Figure 24 (the relatively result of plating tool).
Table 2
| Angle ( *) | Plating tool thickness of the present invention＜the have conical surface 〉 | Compare plating tool thickness＜no conical surface 〉 | ||||||
| The A end face | The B end face | Periphery | Interior week | The A end face | The B end face | | Interior week | |
| 10 | 31.4 | 33.3 | 26.3 | 22.9 | 36.8 | 26.4 | 24.9 | 21.0 |
| 30 | 31.1 | 32.9 | 25.7 | 22.4 | 37.3 | 28.1 | 25.7 | 21.9 |
| 60 | 32.0 | 33.3 | 25.5 | 22.3 | 38.1 | 28.7 | 25.5 | 21.4 |
| 90 | 32.8 | 33.2 | 26.4 | 21.8 | 37.6 | 27.5 | 24.9 | 20.3 |
| 120 | 31.9 | 34.0 | 25.6 | 22.2 | 37.5 | 25.3 | 25.3 | 21.3 |
| 150 | 32.5 | 34.2 | 26.0 | 21.7 | 36.4 | 25.9 | 24.8 | 20.1 |
| 180 | 33.2 | 33.5 | 26.7 | 22.1 | 33.6 | 25.3 | 25.4 | 21.2 |
| 210 | 32.7 | 32.2 | 26.2 | 21.9 | 35.1 | 24.8 | 26.5 | 20.9 |
| 240 | 32.6 | 31.3 | 25.8 | 22.4 | 34.3 | 21.9 | 25.8 | 20.2 |
| 270 | 33.7 | 31.4 | 25.7 | 22.5 | 34.0 | 19.8 | 25.9 | 19.7 |
| 300 | 33.1 | 33.0 | 25.2 | 21.2 | 35.2 | 20.4 | 24.7 | 18.7 |
| 330 | 32.4 | 32.9 | 25.9 | 22.6 | 34.6 | 24.0 | 25.2 | 19.3 |
| On average | 32.5 | 33.0 | 25.9 | 22.2 | 35.9 | 24.8 | 25.4 | 20.5 |
| Deviation | 2.6 | 2.9 | 1.5 | 1.7 | 4.5 | 8.9 | 1.8 | 3.2 |
From table 2 and Figure 23,24, can see, use plating tool 200 of the present invention to carry out the plated product of plating, the film thickness difference of A end face 270a, B end face 270b, periphery 270c and inner peripheral surface 270d is less, simultaneously, also less to the change that causes by certain measuring point, thereby be uniform.In addition, owing to be accompanied by the revolution of supporting pin 234, workpiece 270 is rotated, therefore also not residual tool mark.
In contrast, utilize in the plating of the comparison plating tool that tapering 236a, 236b are not set, A end face 270a and B end face 270b film thickness difference are bigger, can see deviation on thickness, and compare also obviously increase with the situation of having used plating tool 200 of the present invention by the change that measuring point causes.
Though more than with various embodiments the present invention is narrated, the present invention is not limited to described embodiment, in the described scope of invention of the scope of claim, also goes for
Other embodiment.
For example, though (Figure 17) uses the plating tool 200 of electroplating usefulness to be illustrated in described embodiment 5, the structure in workpiece 270 being hung over the support portion 231 that is formed on the axle 210 also can be used for the situation of electroless plating.
Solution and coating method to embodiment 6 describes below.Solution and coating method of the present invention is the technology that comprises following operation, promptly, when the plating that utilizes electrochemical reaction to form the nickel overlay film on the surface of rare-earth bond magnet is handled, to be immersed in the hydrochloric acid of 1～6% concentration 7～25 seconds as the rare-earth bond magnet of plated body and carry out surface-treated surface activation operation, and use the plating bath that contains single nickel salt, nickelous chloride and boric acid to form the plating process of the nickel overlay film of individual layer.
＜surface activation operation 〉
The surface activation operation is the rare-earth bond magnet as plated body is immersed in the hydrochloric acid soln of 1～6% concentration 7～25 seconds and carries out the surface-treated operation.Hydrochloric acid has at short notice the effect that ferric oxide etc. is removed in dissolving, utilizes this effect can dissolve the oxide film of removing the rare-earth bond magnet surface, with the magnet surface sensitization.In this operation, the concentration of employed hydrochloric acid and dipping time concern particularly important.Concentration of hydrochloric acid cross low or situation that dipping time is too short under, the removal of ferric oxide overlay film is just insufficient, might cause the problems such as connecting airtight property reduction of plating, on the contrary, under the long situation of excessive concentration or dipping time, hydrochloric acid can soak into the more rare-earth bond magnet of emptying aperture and the iron partial oxygen of magnet self is melted, thereby becomes the generation reason of iron rust.So for concentration of hydrochloric acid and dipping time, existence can form the specific scope of good plating.In addition, if certain conditions, as described later shown in, also consider the residual good influence that causes by chlorion.According to above reason, in the solution and coating method of the present invention, in the surface activation of rare-earth bond magnet is handled, the condition of 7～25 seconds dip treating is carried out in employing in the hydrochloric acid soln of 1～6% concentration, preferred especially by in the hydrochloric acid soln of 1.5～5.5% concentration, flooding 10～20 seconds, obtain very good nickel plating.
＜plating process 〉
Use contains the plating bath (watt is bathed) of single nickel salt, nickelous chloride and boric acid.In addition, in described plating bath, can also add the semi-gloss additive.As the semi-gloss additive, be not particularly limited, can use material known.
In addition, in the inventive method, do not carry out the multilayer plating, form one-sided nickel overlay film.Usually, in order to improve solidity to corrosion, though two-layer extremely trilaminar multilayer plating is effective, but under the situation of surface activation processing that utilizes hydrochloric acid and the use watt solution and coating method of the present invention of bathing, shown in the embodiment 3, opposite as described later with common convention, confirm that the method for individual layer plating is effective.
＜basic technology example 〉
Figure 25 represents the operation example of electroplating technology of the rare-earth bond magnet of embodiment 6.Present embodiment comprises alkali matting, the 1st washing step, surface activation operation, the 2nd washing step, plating process, the 3rd washing step, hot water wash operation, drying process, and plating is handled and implemented by the rare-earth bond magnet as plated body is applied each operation successively.
It is the alkaline solution (about pH11) of principal constituent that the alkali matting is to use with phosphoric acid salt, carbonate, the operation that the rare-earth bond magnet surface is cleaned.Cleaning is for example used, and 60 ℃ alkaline solution carried out about 1 minute.
Washing step carries out for the sneaking into of soup of the processing that prevents leading portion, in the present embodiment, as shown in figure 25, implements the 1st～the 3rd for totally 3 times.Washing for example can be implemented by the cleaning of at room temperature carrying out repeatedly 2～3 times 30 seconds.
The surface activation operation has foregoing meaning, uses 3.5% hydrochloric acid in the present embodiment, at room temperature implements 1 time 10 seconds dipping.
Plating process uses watt to bathe as previously mentioned, for example under 50 ℃ with current density 2A/dm
2Switched on 40 minutes, and formed 1 layer plating.And the kind of instrument is not particularly limited, and for example can use bracket type, instrument such as hanging.
Below represent the example that operable semi-gloss watt is bathed in the plating process.
In [plating bath formation] 1 liter
Single nickel salt 300g/ liter
Nickelous chloride 50g/ liter
Boric acid 50g/ liter
Semi-gloss additive an amount of (is principal constituent, not sulfur-bearing with fragrant same clan salt)
The pure water remainder part
Hot water wash operation, drying process all are that general ending is handled, and can implement according to well-established law.
＜rare-earth bond magnet plated product 〉
The void content of rare-earth bond magnet of object that becomes plating is preferably below 7 volume %, more preferably below the 3 volume %.And the shape of rare-earth bond magnet, size etc. are not particularly limited, and the magnet of for example cylindric, flat column, cylindric, circular-arc, tabular, crooked all shapes such as tabular all becomes object.
Rare-earth bond magnet as described later shown in, for example rare earth element magnet powder, the binding resin with median size 0.5～50 μ m mixes, and the rare-earth bond magnet that will mix under the temperature more than the softening temperature of this binding resin is shaped with composition and obtains.
Rare-earth bond magnet composition is to contain the following rare earth element magnet powder and the composition of binding resin.
As the rare earth element magnet powder, the preferred material that constitutes by the alloy that contains rare earth element and transition metal, preferred especially following (1)～(5).
(1) will be based on the rare earth element of Sm with based on the transition metal of Co material (hereinafter referred to as Sm-Co class alloy) as basal component.
(2) with R (wherein R is at least a kind that contains in the middle of the rare earth element of Y), based on the transition metal of Fe, B material (hereinafter referred to as R-Fe-B class alloy) as basal component.
(3) will be based on the rare earth element of Sm, based on the transition metal of Fe with based on the material (hereinafter referred to as Sm-Fe-N class alloy) of element between the lattice of N as basal component.
(4) with transition metal such as R (wherein R is at least a kind that contains in the middle of the rare earth element of Y) and Fe as basal component and have the magnetic material (hereinafter referred to as nanocrystal magnet) mutually of nanometer level.
(5) mixed at least 2 kinds material in the middle of the material of composition of described (1)～(4).At this moment, can have the advantage of each ferromagnetic powder of blended simultaneously, thereby obtain better magnetic properties easily.
As the representational material of Sm-Co class alloy, can enumerate SmCo
5, Sm
2TM
17(wherein TM is a transition metal).
As the representational material of R-Fe-B class alloy, can enumerate Nd-Fe-B class alloy, Pr-Fe-B class alloy, Nd-Pr-Fe-B class alloy, Ce-Nd-Fe-B class alloy, Ce-Pr-Nd-Fe-B class alloy, with the part of the Fe in them material after with other transition metal displacements such as Co, Ni etc.
As the representational material of Sm-Fe-N class alloy, can enumerate Sm
2Fe
17Alloy nitrogenize and the Sm that makes
2Fe
17N
3Deng.
As the described rare earth element of ferromagnetic powder, can enumerate Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, cerium mischmetal, can contain they more than a kind or 2 kinds.In addition,, can enumerate Fe, Co, Ni etc. as described transition metal, can contain they more than a kind or 2 kinds.In addition, in order to improve magnetic properties, can also in ferromagnetic powder, as required, contain B, Al, Mo, Cu, Ga, Si, Ti, Ta, Zr, Hf, Ag, Zn etc.
Though the median size of ferromagnetic powder is not particularly limited, about preferred 0.5～50 μ m, more preferably about 1～30 μ m, further about preferred 2～25 μ m.In addition, the size distribution of ferromagnetic powder is preferably to a certain degree to disperse (deviation is arranged).So also can reduce the void content of the binding magnet of gained.And, in [situation more than 2 kinds of promptly mixing described (1)～(4)] under the situation of described (5), also can make its median size difference for the composition of each ferromagnetic powder of blended.
As binding resin, can use thermosetting resin suitably.In general, using under the situation of thermosetting resin as binding resin, compare with the situation of using thermoplastic resin, though the void content of magnet increases easily, but, can reduce the void content of magnet by using the rare-earth bond magnet composition (compound) of condition as described later.
As thermosetting resin, for example can enumerate Resins, epoxy, resol, urea-formaldehyde resin, melamine resin, polyester (unsaturated polyester) resin, polyimide resin, silicone resin, polyurethane resin etc., can use a kind in the middle of them or be mixed with two or more.
In the middle of them, consider preferred epoxy, resol, polyimide resin, silicone resin, special preferred epoxy from the aspect that raising is more remarkable, physical strength is stronger, thermotolerance is better of plasticity.In addition, the Combination of these thermosetting resins and ferromagnetic powder, blended homogeneity are also very good.
And employed thermosetting resin (uncured) can use material or the liquid material that at room temperature is solid-state (Powdered).
The content of aforesaid binding resin powder in rare-earth bond magnet usefulness composition is preferably about 1～10 weight %, more preferably about 1～8 weight %, further preferably about 1～5.5 weight %.When the content of binding resin powder is too much, can't realize the raising of magnetic properties (particularly magnetic energy is long-pending), in addition, when the content of binding resin powder was very few, plasticity reduced, and cannot or hardly be shaped under extreme case.
In addition, rare-earth bond magnet can contain antioxidant with composition.Antioxidant is at rare-earth bond magnet described later during with the mixing of composition etc., the additive that adds in said composition for rotten (the producing owing to the metal ingredient of rare earth element magnet powder plays a role as catalyzer) that prevent that oxidation by the deterioration by oxidation of rare earth element magnet powder or binding resin from causing.The interpolation of this antioxidant can prevent the oxidation of rare earth element magnet powder, help the raising of the magnetic properties of magnet, simultaneously, the raising of rare-earth bond magnet during, the thermostability when also helping to be shaped with the mixing of composition, just can guarantee to bring into play crucial effect aspect the good plasticity with less binding resin amount.
As antioxidant, so long as can suppress the material of the oxidation of rare earth element magnet powder etc., can be any material, for example can use suitably aminated compounds, amino acids, nitrocarboxylic acid compounds, hydrazine class compound, cyano compound, sulfide etc. and metal ion particularly the Fe composition generate the sequestrant of inner complex.
About addition preferred 0.1～2 weight % of rare-earth bond magnet, more preferably about 0.5～1.5 weight % with the antioxidant in the composition.At this moment, the addition of antioxidant is about 10～150% with respect to the addition of binding resin preferably, more preferably about 25～90%.And among the present invention, much less the addition of antioxidant both can not add below the lower value of described scope in addition yet.
Antioxidant is because at rare-earth bond magnet during with the mixing of composition or in the middle of when shaping etc. in the operation, can volatilize or rotten, and therefore in the rare-earth bond magnet of manufacturing, its part exists with residual state.So the content of the antioxidant in the rare-earth bond magnet for example reaches about 10～90% with respect to the addition of rare-earth bond magnet with the antioxidant in the composition, particularly about 20～80%.
Use in the composition at rare-earth bond magnet, as required, for example can add various additives such as softening agent (for example soap, lipid acid such as Zinic stearas) lubricant (for example various inorganic lubricants such as silicone oil, various wax, lipid acid, aluminum oxide, silicon oxide, titanium oxide), stiffening agent, hardening accelerator, other shaping additives.
Rare-earth bond magnet composition is to have mixed described rare earth element magnet powder, binding resin and the mixture of the additives such as antioxidant that add as required maybe mixes this mixture and the material that forms.At this moment, described mixing for example is to use mixing machine such as Henschel mixer, V-arrangement mixing machine or stirrer to carry out.In addition, the mixing of mixture is to use twin shaft for example to extrude that mixing machines such as mixing machine, drum tumbler, kneader carry out.
In addition, though the mixing of mixture can under normal temperature, any condition of high temperature, but preferred temperature more than the softening temperature (softening temperature or glass transition point) of employed binding resin is carried out, and is more preferably carrying out under the temperature more than the softening temperature, below the solidification value and under the incomplete solidified condition of this binding resin.Like this, blended efficient improves, compare with blended situation under the normal temperature, can mix equably with shorter time, simultaneously, owing under the state of the viscosity degradation of binding resin, mix, therefore form binding resin cover the rare earth element magnet powder around state, help rare-earth bond magnet with in the composition and by the reduction of the void content in the magnet of its manufacturing.
And owing to follow the heating etc. of blended material self, mixing temperature changes easily, and therefore the cooling body of for example heating preferably is set, and use can be carried out temperature controlled mixing machine and mix.
Manufacture method to rare-earth bond magnet plated product describes below.At first, rare-earth bond magnet is by modulating described rare-earth bond magnet composition, use said composition, for example making the magnet shape with compression forming method, extrusion molding method or injection molding method and carry out.In the middle of these moulding methodes, compression forming method is the most suitable, below will be to being that the manufacture method of representative describes with the compression forming method.
Make described rare-earth bond magnet with composition (compound), said composition is filled in the mould of compressing forming machine, in magnetic field or do not have a compression molding in the magnetic field.Though this compression molding can be cold conditions shaping (near the shaping normal temperature), warm forming any one, preferred warm forming.That is,, make that the material temperature when being shaped reaches more than the softening temperature of employed binding resin preferably by shaping dies being heated etc.By adopting this kind warm forming, the flowability of the shaped material in the mould improves, and can depress in lower shaping and carry out the good shaping of dimensional precision.Utilize warm forming, for example can be preferably at 50kgf/mm
2Below, more preferably at 35kgf/mm
2Below, further preferably at 20kgf/mm
2Shaping (investing shape) is depressed in following shaping, less to the load that is shaped, shaping is more prone to, simultaneously, even the magnet of ring-type, tabular, crooked shape with thinner wall section such as tabular or longer dimension magnet, also can produce in batches have good and stable shape, the magnet of size.
In addition, by adopting warm forming,, also can reduce the void content of the magnet of gained even depress described low the shaping.In addition, by adopting warm forming, the flowability of the shaped material in the mould improves, the magnetic aligning raising, simultaneously, the reduction of the coercive force of the rare earth element magnet powder during owing to shaping, under the situation about in magnetic field, being shaped, can obtain with apparent on applied the effect identical than the situation of high-intensity magnetic field, therefore, can improve magnetic properties regardless of differently-oriented directivity.After compression molding like this, remove material from shaping dies, promptly obtain rare-earth bond magnet.
The molding of as above compression molding is heated to the temperature more than the solidification value of its thermosetting resin, makes it to solidify.So promptly finish rare-earth bond magnet.The curing of this thermosetting resin also can utilize any one method that directly makes after method that the molding that takes out is heat-treated, the compression molding in shaping dies in the method that die temperature rises from shaping dies.
By utilizing described solution and coating method that the rare-earth bond magnet of as above making is implemented individual layer nickel plating, just can obtain rare-earth bond magnet plated product.
＜effect 〉
Rare-earth bond magnet, is sneaked in the overlay film for fear of chlorion during therefore the surface activation before plating is handled owing to get rusty easily in nature at it, does not use hydrochloric acid, and the not acid of chloride ion-containing such as use sulfuric acid.For example, in No. 3232037 communique of patent, not only from plating bath, get rid of chlorion, and, in surface activation is handled, also use acid ammonium fluoride or hydrofluoric acid etc., and avoid using hydrochloric acid.
In addition, in No. 3232037 communique of patent,, form, do not use common watt to bathe, and use special nickel plating bath without nickelous chloride as nickel plating bath for fear of sneaking into chlorion.
But, the inventor etc. are in view of the low this point of vitriolic oxide film removal effect, after the condition that the surface activation that uses hydrochloric acid is handled has been carried out research, the result who sounds out design is, obtained following understanding, that is, if concentration of hydrochloric acid that uses in handling and treatment time are in specific scope, then can obtain fabulous oxide film removal effect, and be difficult to produce the problem of getting rusty that causes by residual chlorine.Confirm in addition, except the surface activation under given conditions that utilizes hydrochloric acid is handled, bathe by the watt that contains nickelous chloride with use, form the solution and coating method combination of individual layer plating, get rusty or the problem of bubble with regard to not producing, and can form very good nickel overlay film.
Handle by the formation and the surface activation under the specified conditions that have been used in combination watt individual layer plating of bathing, though it is not clear to form the mechanism of good plating at the rare-earth bond magnet surface, if but following consideration then can reasonably illustrate.
At first, in the acid activityization of utilizing hydrochloric acid, by selecting acid concentration and treatment time, in directly getting rusty of avoiding causing, superfluous chlorion residual, can utilize the effect of hydrochloric acid to remove oxide film effectively because of strong acid soaking in the more rare-earth bond magnet of emptying aperture.But,, just can't avoid a spot of chlorion residual on the rare-earth bond magnet surface since use hydrochloric acid.But, when the residual quantity of chlorion more after a little while, just can not cause getting rusty, and can improve near the electroconductibility magnet surface that watt is bathed, thereby might play a role according to the mode of the formation that promotes the nickel film.That is, when having a spot of chlorion, compare with the generation that causes becoming rusty, the most surperficial electroconductibility of magnet that is accompanied by in the plating bath improves, the facilitation effect that overlay film is formed is bigger, thereby infers, can promptly pile up nickel at more recess dispersive rare-earth bond magnet surface.
And, by not adopting multilayer plating (for example forming double-deck overlay film), and the individual layer plating in the bath of employing watt, utilize the energising that continues, in the forming process of nickel overlay film, the chlorion that remains on the rare-earth bond magnet surface is discharged in plating bath gradually, simultaneously, because of the pin hole that disperses to exist the plating that more recess produces also can be along with film forming carrying out disappears.In addition, though in the formation of multilayer overlay film, might reason the 2nd layer the bad grade of film forming causing of the 1st layer surface oxidation etc. and produce iron rust, under the situation of individual layer overlay film, just can not produce this type of problem.According to above reason, in the solution and coating method of the present invention, can obtain the good nickel overlay film of solidity to corrosion.
To enumerate embodiment etc. below, the present invention is described in more detail, but the present invention is not subjected to its any restriction.And, in following experimental example 1～3,, used the magnet made from following method as rare-earth bond magnet.
The manufacturing of＜rare-earth bond magnet 〉
As raw material, prepared rare earth element magnet powder (the quenching Nd of 96.5 weight %
12Fe
78Co
4B
6Powder, median size=19 μ m), the thermosetting resin (Resins, epoxy) of 2.7 weight %, the antioxidant of 0.5 weight %, the lubricant of 0.1 weight %, the softening agent of 0.2 weight %.
Described raw material is mixed, use screw mixer to mix 15 minutes down, be modulated into rare-earth bond magnet set compound at 80～100 ℃.Then, utilize compression molding press,, make contained thermosetting resin curedly, obtained cyclic rare-earth bond magnet thereafter by in 150 ℃ firing furnace, placing 60 minutes with the said composition compression molding.The void content of this rare-earth bond magnet is 4.9%.
Experimental example 1
Affirmation to the influential effect that utilizes the individual layer platingization
＜experimental technique 〉
Solution and coating method is to utilize plating bath structure condition as follows, implements according to the operation of Figure 25.
(1) plating bath A: the semi-gloss plating bath that constitutes by following plating bath
In [plating bath formation] 1 liter
Single nickel salt 300g/ liter
Nickelous chloride 50g/ liter
Boric acid 50g/ liter
Semi-gloss additive an amount of (is the main component and the known additives of sulfur-bearing not with fragrant same clan salt)
The pure water remainder part
(2) plating bath B: the semi-gloss additive in the formation of plating bath A is changed into " gloss additive " (is main component with the aliphatic sulfonate) and an amount of the mixing.
The plating structure condition of plating experiment is as follows.
Individual layer plating (the inventive method 1): with plating bath A under 50 ℃ with current density 2A/dm
2Carried out 40 minutes plating.Consequently, the peripheral part thickness of plated product is 25 μ m.Double-deck plating (comparative approach 1): with plating bath A under 50 ℃ with current density 2A/dm
2Carried out 20 minutes plating., comprise the switching plating bath thereafter, after about 10 seconds, continue with plating bath B under 50 ℃ with current density 2A/dm
2Carried out 20 minutes plating.Consequently, the peripheral part thickness of plated product adds up to 26 μ m.
＜evaluation method 〉
The brine spray experiment:
According to JIS Z2371, the sodium chloride aqueous solution with 5% has carried out 48 hours brine spray.With 10 power microscopes carried out outward appearance observation thereafter.
＜result 〉
In the inventive method 1 of individual layer plating, do not see apparent unusually, formed good plating.On the other hand, in the double-deck plating of comparative approach 1, affirmation has getting rusty from the magnet mother metal in the part.
Experimental example 2
Affirmation to the influential effect of the pre-treatment that utilizes hydrochloric acid:
For the situation of in the surface activation operation, having used hydrochloric acid (the inventive method 2), in the surface activation operation, used the situation (comparative approach 2) of sulfuric acid (being general medicament) as pre-treatment, compare research.
＜experimental technique 〉
Solution and coating method according to the plating process of Figure 25, changes acid-treated condition except the surface activation operation shown in table 3, table 4, test.
＜evaluation method 〉
According to JIS Z2371, the sodium chloride aqueous solution with 5% has carried out 48 hours brine spray.With 10 power microscopes carried out outward appearance observation thereafter.
＜result 〉
The results are shown in table 3 and the table 4.And, the evaluation result in the table record following meaning.
Circle: good (no abnormal in appearance)
Expand: plated film is partly peeled off and the expansible state from mother metal
Rust spot: confirmed to have state from the iron rust of magnet timber in the part
Table 3
Table 4
As can be seen from Table 3, used the surface activation of hydrochloric acid to handle in (the inventive method 2),,, therefore produced plating and the raw-material inequality of connecting airtight, and cause expansion by it because the sensitization on magnet starting material surface is insufficient in lower concentration short period of time side.On the other hand, in the long-time side of high density, the magnet starting material are because the effect of hydrochloric acid and partly form the nuclear (expansion that volumetric expansion that the oxidation by iron causes causes also takes place simultaneously) of iron rust.And, here for convenience, the surface treatment of having used hydrochloric acid is recited as " the inventive method 2 ", still, strictly speaking, only particular concentration of stipulating in the claim scope and the condition of time become object.
On the other hand, used the vitriolic surface activation to handle in (comparative approach 2), the good condition of outward appearance as shown in table 4 does not exist.Because in lower concentration short period of time side, the magnetic iron powder surface is firm ferric oxide, therefore be difficult to carry out sensitization with sulfuric acid, owing to adopt strong acid to change for a long time, ferric oxide is partly peeled off, and therefore infers and also can get rusty simultaneously and expand.
Experimental example 3
Utilize plating bath to constitute the effect that produces:
＜experimental technique 〉
Solution and coating method is implemented according to the plating process of Figure 25 except changing the plating bath condition.
Plating condition A: use the semi-gloss plating bath of the composition shown in the table 5, implement (the inventive method 3) with method with table.
Plating condition B: use the plating bath (not using muriatic electroplate liquid, the general plating bath that uses in electroforming etc.) of the composition shown in the table 5, implement (comparative approach 3) with method with table.
Table 5
| Distinguish | Plating bath constitutes [in 1 liter] | Solution and coating method | |
| A. the present invention (chloride) | Single nickel salt | 300g/L | Electroplate 2A/ |
| Nickelous chloride | 50g/L | ||
| Boric acid | 50g/L | ||
| The semi-gloss additive | In right amount | ||
| Pure water | Remainder | ||
| B. comparative example (no chlorine) | Nickel sulfamic acid | 350g/L | Electroplate 2A/ |
| Boric acid | 40g/L | ||
| Additive * | In right amount | ||
| Pure water | Remainder | ||
*: the main component of additive is that stress is adjusted agent
＜evaluation method 〉
Implement the brine spray identical and test (according to JIS Z2371), similarly estimate with experimental example 1.
＜result 〉
In the inventive method 3, do not see apparent unusually, formed good plating.On the other hand, in comparative approach 3, expansion (plating is partly peeled off and the expansible state from mother metal), rust spot (have in the part from the magnet mother metal the state that gets rusty) have been confirmed.
Experimental example 4
The research of the void content of rare-earth bond magnet
By changing compacting pressure, make beyond void content changes shown in the table 6 as described later, utilize raw material, blending ratio, blending means, manufacturing process, the process for calcining identical with described example, made rare-earth bond magnet.
Specifically, as raw material, prepared rare earth element magnet powder (the quenching Nd of 96.5 weight %
12Fe
78Co
4B
6Powder, median size=19 μ m), the thermosetting resin (Resins, epoxy) of 2.7 weight %, the antioxidant of 0.5 weight %, the lubricant of 0.1 weight %, the softening agent of 0.2 weight %.
These raw materials are mixed, use screw mixer to mix 15 minutes down, be modulated into rare-earth bond magnet set compound at 80～100 ℃.Then, utilize compression molding press with the said composition compression molding.At this moment, by adjusting compacting pressure the void content of magnet is disperseed.
Thereafter by in 150 ℃ firing furnace, placing 60 minutes, make contained thermosetting resin curedly, obtained cyclic rare-earth bond magnet.
＜experimental technique 〉
To the rare-earth bond magnet of gained, utilize plating bath structure condition as follows, implemented plating according to the operation of Figure 25.
Plating bath A: the semi-gloss plating bath that constitutes by following plating bath
In [plating bath formation] 1 liter
Single nickel salt 300g/ liter
Nickelous chloride 50g/ liter
Boric acid 50g/ liter
Semi-gloss additive an amount of (is the main component and the known additives of sulfur-bearing not with fragrant same clan salt)
The pure water remainder part
Use this plating bath A, under 50 ℃ with current density 2A/dm
2Switched on 40 minutes, and formed the individual layer plating.
＜evaluation method 〉
Behind the plating, carried out the outward appearance observation by visual.
＜result 〉
The result is illustrated in the table 6.And the record of the evaluation result in the table has following meaning.In addition, " the peripheral part plating is thick " means the plated thickness of the periphery of the cyclic rare-earth bond magnet plating thing that is used to test.
A: very slick condition of surface (with the plating peer-level on metal parts)
B:, be not obvious coarse condition of surface though do not reach described degree
C: on coating surface, can see some coarse condition of surface
Table 6
| Void content | The peripheral part plated thickness | The outward appearance observations |
| 2.2％ | 26μm | A |
| 3.0％ | 24μm | A |
| 4.1％ | 25μm | B |
| 5.1％ | 25μm | B |
| 5.9％ | 27μm | B |
| 7.0％ | 25μm | B |
| 7.9％ | 26μm | C |
| 8.8％ | 26μm | C |
Can be clear that from table 6, utilize solution and coating method of the present invention,, can obtain good plating for the rare-earth bond magnet of void content below 7 volume %, particularly at void content on the rare-earth bond magnet below the 3 volume %, can form very good overlay film.
Present embodiment can be used for the manufacturing of the plated product of rare-earth bond magnet, and the hard disk that this rare-earth bond magnet plated product for example also can be used as computer uses with electronic unit such as the ringshaped magnet that uses in the motor etc.
Figure 28 is the synoptic diagram of summary of the electroplanting device 400 of explanation embodiments of the present invention 7.This electroplanting device 400 is as main formation, impregnated in an antianode 407,407 and the negative electrode 409 in the plating bath 450 when having the coating bath 401 of filling plating bath, plating, in described coating bath 401, is equipped with a magnet 411.
In the electroplanting device 400, when the workpiece 405 placed in the cage instrument 403 with negative pole part as plated body, workpiece 405 contacts and is energized with negative electrode 409.During plating, produce electrochemical reaction between the workpiece 405 of anode 407 and cathode side, the metal in the plating bath 450 (for example nickel etc.) is separated out to workpiece 405 surfaces and is formed overlay film.
Promptly, contained foreign matter only is under the situation of metal species foreign matter in plating bath 450, even magnetic force is less than 0.25 tesla, because in case after being adsorbed, will become the state of always being caught by magnet 411, therefore can prevent its to workpiece 405 near and attached to its surface.But, be under the situation of organism-metal combination at foreign matter, even utilize the magnetic force of magnet 411 that it is adsorbed, if but magnetic force a little less than, then because and the effect of the liquid stream of plating bath 450 etc., thereby will break away from very simply.Can not catch under the situation of organism-metal combinations with magnet 411, foreign matter suspends in liquid, because of electro ultrafiltration attached on the workpiece 405, become the reason that causes pin hole.
In the present embodiment,, be not limited to this configuration though magnet 411 is configured in the inner bottom part of coating bath 401.For example, preferably according to the kind of the instrument 403 of supporting workpiece 405 and the selected suitable position of size of coating bath 401.In addition because the purpose of magnet 411 is to catch to the close organism-metal combination of workpiece 405, therefore preferably be configured in as far as possible with the close position of workpiece 405 on.
In the electroplanting device 400 of present embodiment, except described formation, as required, can set up be used in coating bath 401 with the whipping appts of plating bath 450 homogenizing, be used to improve plating efficient heating unit or refrigerating unit, be used to remove the filtration unit etc. of the foreign matter of plating bath.
Solution and coating method of the present invention can be implemented according to common plating process and condition.If enumerate the summary situation when utilizing the inventive method to electroplate, then at first, workpiece 405 is positioned on the instrument 403, after having carried out cleaning according to necessity, under specific currents, carry out tarnish plating or semi-gloss plating or gloss and electroplate.The plating thing by carrying out drying, promptly obtains final plated product after cleaning.
As workpiece 405 as plated body, though be not particularly limited, can be metal, also can be nonmetal, can also be metal and nonmetallic mixture or the metal that has emptying aperture etc.As the example of workpiece 405, can enumerate mixture, casting alloy of the employed sintered alloy of precise part, resin and powder metal etc., more particularly, can enumerate for example sintered magnet, binding magnet, casting magnet etc.
Electro-plating method of the present invention can form plating very uniformly with easy utensil, also can not produce simultaneously by foreign matter and adhere to and the defective of the plating that causes, therefore, for example the hard disk of suitable computer etc. require the plating of employed workpiece 405 in the purposes such as high dimensional accuracy, high antirust, anti-dusting with the ringshaped magnet that uses in the motor etc.
(embodiment)
Utilize embodiment, comparative example that present embodiment is described in more details below, but the present invention is limited by them.
The configuration surface magneticflux-density under following condition, has been implemented plating and anti-corrosion experiment at the magnet of 0.25 tesla (below be labeled as " 0.25T ") in coating bath.Its result is illustrated in the table 7.
＜plated body 〉
For plated body, used the cyclic n nitroso compound d-Fe-B class binding magnet of external diameter 19mm, internal diameter 17mm, high 4mm.
＜plating condition 〉
Plated body is positioned in the analog bracket formula plating tool, after cleaning, uses 50 ℃ matt watt to bathe, with 2A/dm
2Carried out 30 minutes matt plating, bathed with 50 ℃ gloss watt then, with 2A/dm
2Having carried out 20 minutes gloss electroplates.The plated product of gained carries out drying after having carried out cleanings such as the cleaning of ultrasonic wave water, hot water cleaning.
＜anti-corrosion experiment 〉
According to JIS Z2371, the sodium chloride aqueous solution with 5% has carried out 48 hours brine spray.With 10 power microscopes confirmed have or not got rusty thereafter.
Embodiment 2,3
Except having used the different magnet of magnetic force, identical with embodiment 1, carried out plating, studied solidity to corrosion.Among the embodiment 2, surface magnetic flux density is made as 0.30T, and among the embodiment 3, surface magnetic flux density is made as 0.35T.Its result is illustrated in the table 7 in the lump.
Comparative example 1～4
Except having used the different magnet of magnetic force, identical with embodiment 1, carried out plating, studied solidity to corrosion.In the comparative example 1, surface magnetic flux density is made as 0.05T, and in the comparative example 2, surface magnetic flux density is made as 0.10T, and in the comparative example 3, surface magnetic flux density is made as 0.15T, and in the comparative example 4, surface magnetic flux density is made as 0.20T.Its result is illustrated in the table 7 in the lump.
Table 7
| Absorption magnet surface magneticflux-density (T) | The brine spray experimental result | |||
| Drop into number | The number of getting rusty | Scale rate (%) | ||
| Comparative example 1 | 0.05 | 50 | 8 | 16.0 |
| Comparative example 2 | 0.10 | 50 | 9 | 18.0 |
| Comparative example 3 | 0.15 | 50 | 7 | 14.0 |
| Comparative example 4 | 0.20 | 50 | 4 | 8.0 |
| | 0.25 | 50 | 0 | 0 |
| Embodiment 2 | 0.30 | 50 | 0 | 0 |
| Embodiment 3 | 0.35 | 50 | 0 | 0 |
Can see from above result, by with surface magnetic flux density in the magnet configuration more than the 0.25T in plating bath, can prevent from fully basically to get rusty.
Comparative example 5
Except in coating bath with distributing style shown in Figure 29, having disposed surface magnetic flux density is beyond 6 magnet 15a～15f of 0.13～0.15T, with the embodiment 1 identical plating that carried out.Behind the plating, after magnet being taken out, studied the attachment state of the foreign matter (organism-metal combination) that is captured, find foreign matter adhering on magnet to be trace.In addition,, carried out the anti-corrosion experiment identical, produced the phenomenon of getting rusty with embodiment 1 for formed plating.
This situation shows, when the magnetic force of magnet is more weak, even configuration is a plurality of in coating bath, also can't obtain effect basically.
Though more than with various embodiments the present invention is narrated, the present invention is not limited to described embodiment, in the scope of invention that the claim scope is recorded and narrated, also can be suitable for for other embodiment.
For example,, be not limited thereto, for example in hanging instrument, rotary bracket formula instrument, drum-type instrument etc.,, also can obtain identical action effect by distributed magnet 11 though the embodiment of Figure 28 uses analog bracket formula instrument.
Claims (9)
1. a plating tool is used for the cyclic plated body is carried out plating, it is characterized in that,
Have the support portion of supporting described plated body,
Described support portion is by according to being that the mode that revolves round the sun in the center disposes with the rotation axis,
Described support portion has when supporting described plated body the contact surface that contacts with the inner peripheral surface of described plated body and support,
Described support portion has the inclined wall that limits from the position to plated body that the both sides extension of described contact surface is provided with.
2. plating tool according to claim 1 is characterized in that, also having with described rotation axis is the base portion that center of rotation is rotated, and described support portion is used as to be located at the projection on the described base portion and to form.
3. plating tool according to claim 2 is characterized in that, is provided with a plurality of described support portions, and the described rotation axis that is configured to described base portion is a central circular.
4. plating tool according to claim 2 is characterized in that, described support portion have prevent plated body come off come off and prevent member.
5. plating tool according to claim 4 is characterized in that, described coming off prevents that member is used as the plectane on the cephalic par of being located at described projection and forms.
6. plating tool according to claim 5 is characterized in that the diameter of described plectane is less than the internal diameter of plated body.
7. plating tool according to claim 1 is characterized in that, described support portion is used as the electroconductive member setting that electric current is provided to described plated body.
8. a solution and coating method uses Accessory Right to require any described plating tool in 1 to 7, and the cyclic plated body is carried out plating.
9. an electroplanting device is characterized in that, has any described plating tool in the Accessory Right requirement 1 to 7.
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| JP2003191570A JP2005023389A (en) | 2003-07-04 | 2003-07-04 | Electroplating method, and electroplating apparatus |
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| JP4965959B2 (en) * | 2005-10-25 | 2012-07-04 | 株式会社荏原製作所 | Electroless plating equipment |
| CN104480506B (en) * | 2014-12-05 | 2016-12-07 | 宁波韵升股份有限公司 | A kind of electroplating technology of neodymium iron boron thin slice annular products |
| CN109143421B (en) * | 2018-06-27 | 2022-09-27 | 深圳市锦瑞新材料股份有限公司 | Deplating process |
| CN110318076A (en) * | 2019-07-17 | 2019-10-11 | 安徽启明表面技术有限公司 | The preparation method of zinc-plating brightener |
| CN112593217A (en) * | 2020-11-26 | 2021-04-02 | 陈国� | A high-efficient reaction unit for metal plating |
| CN115976614A (en) * | 2021-10-14 | 2023-04-18 | 欣兴电子股份有限公司 | Electroplating apparatus and electroplating method |
| US11686008B2 (en) | 2021-10-14 | 2023-06-27 | Unimicron Technology Corp. | Electroplating apparatus and electroplating method |
| CN114481276A (en) * | 2022-02-08 | 2022-05-13 | 江西荧光磁业有限公司 | Electroplating device and method for surface corrosion resistance double-coating of neodymium iron boron magnet |
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2003
- 2003-07-04 JP JP2003191570A patent/JP2005023389A/en active Pending
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2004
- 2004-07-05 CN CN 200610136180 patent/CN1958871A/en active Pending
- 2004-07-05 CN CN 200610136181 patent/CN1958865A/en active Pending
- 2004-07-05 CN CN 200610136182 patent/CN1958873A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005023389A (en) | 2005-01-27 |
| CN1958873A (en) | 2007-05-09 |
| CN1958865A (en) | 2007-05-09 |
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