JP2002088468A - Method for suppressing generation of projection in metal vapor deposited film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for effectively suppressing the generation of projections on a metal vapor-deposited film of aluminum or zinc when the film is formed on a surface of a work such as rare earth permanent magnet. SOLUTION: When a metal vapor deposition material is vapor-deposited on a surface of a work while rotating an accommodating member and/or a holding member around the axis of rotation in the horizontal direction by using a vapor deposition apparatus having a vaporization unit of the vapor deposition material and the accommodating member and/or the holding member for accommodating and/or holding the work, Vickers hardness of the film formed on the surface of the work is maintained to be >=25.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention suppresses the formation of projections on a metal-deposited film such as aluminum or zinc formed on the surface of a workpiece such as a rare-earth permanent magnet. About the method.

[0002]

2. Description of the Related Art Rare-earth permanent magnets such as R-Fe-B permanent magnets represented by Nd-Fe-B permanent magnets have high magnetic properties, and are used in various fields today. I have. However, rare-earth permanent magnets include metal species (particularly R) that are susceptible to oxidative corrosion in the atmosphere. Therefore, when used without performing surface treatment, corrosion proceeds from the surface due to the influence of a slight acid, alkali, moisture, etc., and rust is generated, which leads to deterioration and variation in magnetic characteristics. Will be. Further, when rust is generated on a magnet incorporated in a device such as a magnetic circuit, the rust may scatter and contaminate peripheral components. In view of the above, for the purpose of imparting excellent corrosion resistance to a rare-earth permanent magnet, a metal vapor-deposited film of aluminum, zinc, or the like is formed on the surface thereof. In particular, the aluminum coating has excellent corrosion resistance and mass productivity, and also has excellent adhesion reliability with the adhesive required when assembling parts (the coating must reach the breaking strength inherent in the adhesive). And the adhesive is hardly peeled off), so that it is widely applied to rare-earth permanent magnets requiring strong adhesive strength. As the adhesive, epoxy resin, phenol resin, reactive acrylic resin, modified acrylic resin (ultraviolet curing adhesive or anaerobic adhesive), cyanoacrylate resin, silicone resin, polyisocyanate Emulsion type bonding of various resin adhesives such as vinyl acetate resin, methacrylic resin, polyamide and polyether, and various resin adhesives (for example, vinyl acetate resin adhesive and acrylic resin adhesive) Agents, various rubber-based adhesives (for example, nitrile rubber-based adhesives and polyurethane rubber-based adhesives), ceramics adhesives, and the like are appropriately selected and used according to the purpose of heat resistance, impact resistance, and the like. As an apparatus used for forming a metal deposition film on the surface of a rare earth permanent magnet, for example, US Pat.
No. 16161 and Graham Legge: "Ion Vapor Deposit
ed Coatings for Improved Corrosion Protection ": Re
printed from Industrial Heating, September, 135-14
0, 1994. FIG. 1 is a schematic front view (partially transparent view) of the inside of a vacuum processing chamber 1 connected to an unillustrated evacuation system of the example. Above the room, for example, two cylindrical barrels 5 formed of a stainless steel mesh wire net are rotatably provided around a rotary shaft 6 on a horizontal rotation axis. Below the room, a plurality of boats 2 as evaporating units for evaporating aluminum as a metal vapor deposition material are arranged on a boat support table 4 erected on a support table 3. According to this device, a plurality of rare-earth permanent magnets 30 to be processed are accommodated in the cylindrical barrel 5, and the cylindrical barrel is rotated around the rotating shaft 6 as indicated by an arrow while rotating, as shown in FIG. Aluminum is evaporated from the boat 2 heated to a predetermined temperature by a substantially heating means, and an aluminum vapor-deposited film is formed on the surface of the rare-earth permanent magnet 30 in the cylindrical barrel 5.

[0003]

The vapor deposition apparatus shown in FIG. 1 is capable of performing a large amount of processing and is excellent in productivity. However, in some cases, projections may be formed on the metal deposition film formed on the surface of the rare earth permanent magnet. The presence of such protrusions in the coating has a detrimental effect on adhesion when the magnet is incorporated into the component using an adhesive. In particular, the height of the protrusion is JIS B0601-
If the average value exceeds 100 μm from the average value of the roughness curve in 1994, the thickness of the adhesive must be considerably increased in order to avoid the influence of the presence of the protrusions and secure a sufficient adhesive force. I can't get it. Therefore, when a low-viscosity adhesive is used, a sufficient thickness cannot be secured, and as a result, sufficient adhesive strength cannot be obtained. Also, when using an adhesive that cures through a chemical reaction with the film surface, such as a cyanoacrylate adhesive,
The curing does not occur sufficiently, and as a result, sufficient adhesive strength cannot be obtained. Furthermore, embedded magnets (IP
Even when an adhesive is not used, such as when a magnet is incorporated into an M) type motor, the dimensional accuracy of the component cannot be increased due to the presence of the protrusion, and as a result, the size and accuracy of the component have been increased in recent years. It is difficult to respond to the demands.
Therefore, in the present invention, when a metal vapor-deposited film such as aluminum or zinc is formed on the surface of an object to be processed such as a rare-earth permanent magnet, a method for effectively suppressing the formation of protrusions in the film is provided. The purpose is to provide.

[0004]

Means for Solving the Problems The present inventors have analyzed and studied in detail why and how projections are formed on a metal vapor-deposited film and found the following facts.
That is, in the vapor deposition apparatus as shown in FIG.
The rotation of the cylindrical barrel causes, within the barrel, phenomena such as collision and rubbing between the rare-earth permanent magnets housed in the barrel, and collision and rubbing between the magnet and the barrel wall surface. The metal deposition film formed on the surface is damaged, a part of it is shaved, and the cut pieces are rubbed with a magnet etc. to be granulated and adhere to other film parts, and a further film is formed thereon Thus, a peening process (for example, disclosed in Japanese Patent Application Laid-Open No.
212), the magnets are always heated by the radiant heat from the evaporating section, and the magnets are unnecessarily increased due to this. It has been found that the metal vapor-deposited film formed on the surface is softened by the temperature rise, and is easily damaged.

[0005] The present invention has been made based on the above findings, and a method for suppressing the formation of projections in a metal deposition film according to the present invention is as follows.
Using a vapor deposition apparatus having a vapor deposition material evaporation section and a housing member and / or a holding member for housing and / or holding an object to be processed, the housing member and / or the holding member are rotated in a horizontal rotation axis. When the metal deposition material is deposited on the surface of the object to be processed while being rotated to the center, the Vickers hardness of the coating formed on the surface of the object to be processed is maintained at 25 or more. According to a second aspect of the present invention, in the method according to the first aspect, the temperature of the processing object stored and / or held in the housing member and / or the holding member is set to the melting point (Tm) in the bulk of the metal vapor deposition material. (° C.) or less, the Vickers hardness of the film formed on the surface of the object to be treated is 25.
It is characterized by maintaining above. Further, in the method according to the third aspect, in the method according to the second aspect, the metal deposition material is aluminum and the temperature of the object to be processed is 350 ° C.
It is characterized in that the evaporation is performed while maintaining below. According to a fourth aspect of the present invention, in the method of the second aspect, the metal deposition material is zinc, and the temperature of the object to be processed is set to 250.
It is characterized in that the deposition is carried out at a temperature of not more than ℃. Also,
A method according to a fifth aspect is characterized in that, in the method according to any one of the first to fourth aspects, the vapor deposition is performed by a vacuum vapor deposition method or an ion plating method. A method according to a sixth aspect is characterized in that, in the method according to any one of the first to fifth aspects, the housing member and / or the holding member are configured to be detachable. A method according to a seventh aspect is characterized in that, in the method according to any one of the first to sixth aspects, the housing member is a cylindrical barrel formed of a mesh. The method according to claim 8 is the method according to claim 7, wherein the cylindrical barrel is capable of revolving around a rotation axis of a horizontal direction. It is supported, and revolves around the rotation axis of the support member by rotating the support member.
According to a ninth aspect of the present invention, in the method according to the eighth aspect, the cylindrical barrel and / or a supporting member for supporting the cylindrical barrel are detachably configured. According to a tenth aspect of the present invention, in the method of the eighth aspect, a plurality of the cylindrical barrels are annularly supported outward in the circumferential direction of the rotation axis of the support member. The method according to claim 11 is the same as the method according to claim 7.
The method according to any one of the preceding claims, wherein the inside of the cylindrical barrel is divided to form two or more receiving portions.
A method according to a twelfth aspect is characterized in that, in the method according to the eleventh aspect, the inside of the cylindrical barrel is radially divided from a rotation axis to form two or more housing portions. A method according to a thirteenth aspect is characterized in that, in the method according to any one of the first to twelfth aspects, the object to be processed is a rare-earth permanent magnet. According to a fourteenth aspect of the present invention, there is provided a rare-earth permanent magnet having a metal vapor-deposited film in which the formation of projections is suppressed by the method of the thirteenth aspect. Claim 15
The rare earth-based permanent magnet according to the present invention is characterized in that, in the rare-earth permanent magnet according to the fourteenth aspect, the height of the protrusions present in the metal deposition film is 100 μm or less from the average line of the roughness curve in JIS B0601-1994. And

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION According to the method of the present invention for suppressing the formation of projections in a metal vapor-deposited film, an evaporating portion of a vapor-deposition material, a housing member for housing and / or holding an object to be processed and / or Alternatively, when the metal deposition material is vapor-deposited on the surface of the object to be processed while rotating the housing member and / or the holding member around a horizontal rotation axis using a vapor deposition device having a holding member, The vapor deposition is performed while maintaining the Vickers hardness of the coating formed on the surface of the substrate at 25 or more.

That is, the present invention maintains the Vickers hardness of the film formed on the surface of the object to be treated at 25 or more by performing the vapor deposition while suppressing the temperature rise of the object to be treated more than necessary. The coating is softened to prevent the workpieces from colliding or rubbing each other, and from being easily damaged by the collision or rubbing between the workpiece and the barrel wall surface. As a result, protrusions are formed on the formed coating. This is based on the finding that it can be effectively suppressed.

In the present invention, an object to be formed with a metal vapor-deposited film is not particularly limited as long as it can form a metal vapor-deposited film, but the present invention has a strong magnetic force. Therefore, the present invention is particularly effective for rare-earth permanent magnets that require a high adhesive strength with an adhesive when incorporated into a component.

The metal deposition material applied in the present invention is not particularly limited.
Since the melting point is low, aluminum, zinc, tin,
This is effective when applied to lead, bismuth, and alloys containing at least one of these metal components.

In the present invention, in order to carry out vapor deposition while maintaining the Vickers hardness of the film formed on the surface of the object to be treated at 25 or more, the temperature of the object accommodated or held in the accommodation member or the holding member is required. Is maintained at ２ or less of the melting point (Tm) (° C.) of the bulk of the metal deposition material. The melting point in the bulk of the above metal vapor deposition material is 660 ° C. for aluminum and 420 for zinc, respectively.
℃, tin 232 ° C, lead 328 ° C, bismuth 271 ° C
It is. In the case of an alloy, when a two-phase coexistence state of a solid phase and a liquid phase exists at a high temperature, the melting point is the solidus temperature in the composition. When the object to be processed is a rare earth permanent magnet, aluminum and zinc are preferable as metal deposition materials in view of cost. When aluminum is used, the deposition may be performed while maintaining the temperature of the magnet at 2/3 or less of the melting point of the bulk of aluminum, that is, 440 ° C. or less. Desirably, it is more desirable to perform the vapor deposition while maintaining the temperature at 300 ° C. or lower. When zinc is used, the temperature of the magnet is set to ２ or less of the melting point of the bulk zinc, that is, 280.
The deposition may be carried out at a temperature of not more than 250C, but it is desirable to carry out the deposition at a temperature of not more than 250C. When the object to be processed is a rare earth permanent magnet, the lower limit of the temperature of the object to be processed is generally 100 ° C. If the deposition is performed at a temperature lower than 100 ° C., sufficient adhesion may not be obtained between the magnet and the metal deposition film.

[0011] The method for suppressing the formation of protrusions in the metal deposition film of the present invention includes a vacuum deposition method, an ion plating method,
Suitable for vapor deposition methods such as the beam method and the CVD method, that is, a method in which the temperature of an object to be processed rises more than necessary during vapor deposition, and as a result, projections may be generated in a coating film. Is done. Above all, a vapor deposition method using a resistance heating method, such as a vacuum vapor deposition method or an ion plating method, particularly a vapor deposition method using a method of continuously supplying and dissolving a vapor deposition material to an evaporating section heated and energized, has a high quality. Although film formation at a film speed is possible and is useful for large-scale processing, by applying the method for suppressing the formation of projections of the present invention to such a vapor deposition method, a film of excellent quality can be stably and efficiently produced. The effect of being able to be formed on the surface of the object to be treated is achieved.

In the vacuum processing chamber applied in the present invention, there is provided a vaporizing material evaporation section and a housing member for housing an object to be processed, and the housing member is rotated about a horizontal rotation axis. Examples of a vapor deposition apparatus that can vapor-deposit a vapor deposition material on the surface of a processing object include the following apparatuses.

An example is the vapor deposition apparatus shown in FIG. When such an apparatus is used, as a method of performing vapor deposition while maintaining the Vickers hardness of the coating formed on the surface of the processing object at 25 or more, the temperature of the processing object stored in the cylindrical barrel is A method of completing vapor deposition until the melting point (Tm) (° C.) in the bulk of the metal vapor deposition material reaches ３, temporarily suspending vapor deposition until the temperature reaches ２ of the melting point, and cooling the object to be processed. After that, the vapor deposition is restarted and repeated, a method of introducing a cooling mechanism using cooling water or a cooling gas into the cylindrical barrel, and maintaining the temperature of the object to be processed at a temperature equal to or lower than ／ of the melting point. There is a method of arranging a shielding plate for suppressing radiant heat from the evaporator.

Further, if a vapor deposition apparatus as shown in FIG. 2 is used, it is possible to effectively suppress the temperature of the object to be processed from rising more than necessary, and it is possible to prevent the film formed on the surface of the object from being processed. The deposition can be easily performed while maintaining the Vickers hardness at 25 or more.

FIG. 2 is a schematic front view (partially transparent view) of the inside of a vacuum processing chamber 51 connected to an unillustrated evacuation system (apparatus for forming a vapor-deposited aluminum film on the surface of a rare-earth permanent magnet). Will be described as an example). At the upper part of the room, two support members 57 rotatable about a rotation shaft 56 on a horizontal rotation axis are provided side by side.
A plurality of cylindrical barrels 55 made of, for example, a stainless steel mesh wire mesh are supported by a support shaft 58 so as to be able to revolve in an annular shape. A plurality of boats 52, which are evaporating units for evaporating the metal deposition material, are arranged below a room on a boat support 54 standing upright on a support table 53. Inside the lower part of the support table 53, an aluminum wire 59 which is a metal deposition material is wound and held on a payout reel 60. Aluminum wire 5
The tip of 9 is guided above the boat 52 by a heat-resistant protective tube 61 facing the inner surface of the boat 52. A cutout window 62 is provided in a part of the protection tube 61.
The feeding gear 63 provided corresponding to the cutout window 62 is directly in contact with the aluminum wire 59, and the aluminum wire 59 is fed so that aluminum is constantly supplied into the boat 52. Have been.

FIG. 3 shows a support member 57 rotatable about a rotation shaft 56 on a horizontal rotation axis, which is formed of six stainless steel mesh nets on the outer side in the circumferential direction of the rotation shaft 56. FIG. 9 is a schematic perspective view showing that the cylindrical barrel 55 is revolvingly supported in an annular shape by a support shaft 58 (the total number of supported cylindrical barrels is 12 because they are supported in two stations). (The magnet is not accommodated.)

When the support member 57 is rotated about the rotation shaft 56 (see the arrow in FIG. 2), the cylindrical barrel 55 supported by the support shaft 58 on the support member 57 is provided on the outer side of the rotation shaft 56 in the circumferential direction. Correspondingly, the revolving motion is made around the rotating shaft 56. As a result, the distance between each cylindrical barrel and the evaporator disposed below the support member fluctuates, and the following effects are exhibited. That is, the cylindrical barrel located at the lower part of the support member 57 is approaching the evaporator. Therefore, a metal vapor-deposited film is efficiently formed on the surface of the rare-earth permanent magnet 80 housed in the cylindrical barrel. On the other hand, the temperature rise of the rare-earth permanent magnet accommodated in the cylindrical barrel away from the evaporator is suppressed by the distance from the evaporator. Therefore, during this time, the softening of the metal deposition film formed on the surface is suppressed. Thus, if this vapor deposition device is used, it is possible to simultaneously achieve efficient formation of the metal vapor deposition film and suppression of softening of the formed metal vapor deposition film,
Protrusion formation can be effectively suppressed.

This vapor deposition apparatus is advantageous in that it exhibits the above-mentioned effects and has the following advantages. That is, even when performing a large amount of processing, it is better to store a small amount in each cylindrical barrel in this vapor deposition apparatus than to store a large amount of magnets in one cylindrical barrel as in the vapor deposition apparatus shown in FIG. Since the number of collisions and the number of rubs between the magnets in the barrel can be reduced, it is possible to further suppress the generation of protrusions due to damage to the coating. Also, like bow-shaped magnets and large magnets,
When the vapor deposition apparatus shown in FIG. 1 is accommodated in a cylindrical barrel having a large R (radius of curvature) and subjected to vapor deposition, the magnet slides down along the inner surface of the barrel, and the coating is easily damaged by friction with the inner surface of the barrel. However, since the agitation can be uniformly performed by accommodating each small R cylindrical barrel in the vapor deposition apparatus and performing the vapor deposition processing, the generation of protrusions due to damage to the coating film is further suppressed. It is possible to do. Conventionally, in order to reduce the number of collisions or rubbing between magnets, a method of using a dummy (for example, a ceramic ball having a diameter of 10 mm) which has been housed together with the magnet in the barrel has been used. Although there was a case where it was adopted, the necessity was eliminated by using this vapor deposition apparatus, and the efficiency of forming a film on the magnet could be improved.
2 of melting point (Tm) (° C) in bulk of metal deposition material
It becomes easy to complete the vapor deposition before reaching / 3.

In the vapor deposition apparatus shown in FIGS. 2 and 3, a cylindrical barrel 55 is provided above the vacuum processing chamber 51.
Is disposed, and the boat 52 as an evaporator is disposed below the room. However, the positional relationship between the support member and the evaporator is not limited to this positional relationship. By rotating the support member and the evaporator, if the positional relationship between the cylindrical barrel and the evaporator is variable, the support member and the evaporator may be arranged at any position in the vacuum processing chamber. I don't care. However, if the evaporator is disposed outside the support member, the distance between the support member and the evaporator can be set in a wide range in the internal space of the vacuum processing chamber. It is possible to easily set the desired distance in order to suppress the softening of the formed film and the initial formation, and also in the case of forming a vapor deposition film by evaporating the metal vapor deposition material while melting it, The arrangement of each member can be easily set, and the handling is excellent. Further, in the vapor deposition apparatus shown in FIGS. 2 and 3, six cylindrical barrels 55 are supported on one surface of one support member 57. The total number of barrels is 12), and the number of cylindrical barrels supported by the support member is not limited to this, and may be one. Further, the cylindrical barrel 55 may be supported so as to revolve around the rotation shaft 56 of the support member 57 by rotating the support shaft 58 and to rotate by a mechanism known per se.

Further, even if a vapor deposition apparatus as shown in FIG. 4 is used, it is possible to effectively suppress the temperature of the object to be processed from unnecessarily increasing, and to form a film formed on the surface of the object to be processed. Can be easily deposited while maintaining Vickers hardness of 25 or more.

FIG. 4 is a schematic front view (partially transparent view) of the inside of a vacuum processing chamber 101 connected to an unillustrated evacuation system (apparatus for forming a vapor-deposited aluminum film on the surface of a rare-earth permanent magnet). Will be described as an example). In the upper part of the room, for example, two cylindrical barrels 105 formed of a stainless steel mesh wire net and rotatable around a rotation shaft 106 on a horizontal rotation axis are provided. The cylindrical barrel 105 is internally divided into six parts radially from the rotation axis to form a fan-shaped accommodation section. A plurality of boats 102, which are evaporating units for evaporating a metal deposition material, are arranged below a room on a boat support 104 standing upright on a support table 103. Inside the lower part of the support table 103, an aluminum wire 109, which is a metal deposition material, is wound and held on a payout reel 110. The tip of the aluminum wire 109 is guided above the boat 102 by a heat-resistant protective tube 111 facing the inner surface of the boat 102. A notch window 112 is provided in a part of the protection tube 111.
The feeding gear 113 provided corresponding to 2 is directly in contact with the aluminum wire 109, and the aluminum wire 109 is fed so that aluminum is constantly supplied into the boat 102.

FIG. 5 shows a rotating shaft 106 formed of a stainless steel mesh wire mesh on a horizontal rotating axis.
FIG. 9 is a schematic perspective view showing a cylindrical barrel 105 that is rotatable around a shaft and has a housing portion having a fan-shaped cross section formed by radially dividing the inside into six from the rotation axis (magnets are not housed).

When the cylindrical barrel 105 is rotated about the rotary shaft 106 (see the arrow in FIG. 4), the space between the individual storage portions formed inside the cylindrical barrel and the evaporating portion disposed below the storage portions is reduced. Is varied, and similarly to the case where the vapor deposition is performed using the vapor deposition apparatus shown in FIGS. 2 and 3, the generation of protrusions can be effectively suppressed.

In the vapor deposition apparatus shown in FIGS. 4 and 5, a cylindrical barrel 105 in which the inside is radially divided into six parts from the rotation axis above the vacuum processing chamber 101 to form a fan-shaped receiving section. Is disposed, and the boat 102 as the evaporating section is disposed below the room. However, the positional relationship between the cylindrical barrel and the evaporating section is not limited to this positional relation, and the cylindrical barrel is rotated. By
The cylindrical barrel and the evaporating section may be arranged at any position in the vacuum processing chamber as long as the positional relationship between the storage section and the evaporating section is variable. In addition, in the vapor deposition apparatus shown in FIGS. 4 and 5, the inside of the cylindrical barrel is radially divided into six from the rotation axis to form a receiving section having a fan-shaped cross section, but is formed inside the cylindrical barrel. The storage portion may be formed in any divided form as long as the distance between the storage portion and the evaporating portion is made variable by rotating the cylindrical barrel. .

The shape of the barrel as a housing member in the above vapor deposition apparatus is not limited to a cylindrical shape as long as it is a cylindrical shape, and may be a polygonal cylindrical shape such as a hexagonal or octagonal cross section. Good. Examples of the mesh include a mesh wire mesh made of stainless steel or titanium. Stainless steel or titanium is desirable as the material of the mesh because of its excellent material strength and its excellent durability against etching and stripping liquids such as alkaline aqueous solution used for the work of removing vapor deposition material attached to the barrel. is there. The mesh may be created using a mesh plate obtained by punching or etching a flat plate, or may be created by knitting a linear body. Further, the aperture ratio of the mesh (the ratio of the area of the opening to the area of the mesh) also depends on the shape and size of the object, but improves the efficiency of forming a film on the object,
In order to easily complete the vapor deposition until the temperature of the object to be processed reaches ／ of the melting point (Tm) (° C.) of the bulk of the metal vapor deposition material, the temperature is preferably 50% or more.
More preferably, it is 0% or more. The upper limit of the aperture ratio is not particularly limited, but if it is larger than 95%, the mesh may be deformed or damaged at the time of vapor deposition processing or other handling. Desirably, 85% or less is more desirable. The wire diameter of the mesh is selected in consideration of the aperture ratio and strength, but is generally preferably 0.1 mm to 10 mm. Further, considering the ease of handling, etc., 0.
3 mm to 5 mm is more desirable.

In the vacuum processing chamber applied in the present invention, an evaporating portion of a deposition material and a holding member for holding an object to be processed are provided, and the holding member is rotated around a horizontal rotation axis. As an example of an evaporation apparatus capable of depositing an evaporation material on the surface of an object to be processed, an apparatus using a jig shown in FIG. 6 instead of a cylindrical barrel in the apparatus shown in FIG. That is, an object 190 having a hollow portion such as a ring-shaped magnet as a holding member is provided on the outer side in the circumferential direction of the rotation shaft 156 of the support member 157 which is rotatable about the rotation shaft 156 on the horizontal rotation axis. A device in which a suspending member 160 for suspension is revolvably supported, and the suspending member 160 revolves around a rotating shaft 156 of the supporting member 157 by rotating the supporting member 157 is exemplified. When vapor deposition is performed using such an apparatus, friction occurs between a suspended member and an inner peripheral surface that is a contact portion of the object to be processed suspended by the member with the member. The metallized coating formed on is damaged, a part of the metallized coating is shaved, and the further cut pieces are rubbed with the suspending member to be granulated and adhere to other coating portions, thereby forming a further coating thereon. This may result in an unremovable protrusion. Therefore, even when performing vapor deposition using such an apparatus, the effect of the present invention can be obtained by performing vapor deposition while maintaining the Vickers hardness of the coating formed on the surface of the object to be processed at 25 or more.

In the above-described vapor deposition apparatus, the following advantages are obtained when the accommodating member and the holding member are configured to be detachable from the support member, and when the support member is configured to be detachable from the vacuum processing chamber. In other words, it is possible to carry out the loading and unloading of the processing object at an arbitrary place, so that the convenience is improved. Usually, when one vapor deposition process is completed, the housing member and the holding member themselves are heated to a high temperature. When the next vapor deposition process is performed using the holding member or the holding member in this state, there is a possibility that the temperature of the object to be processed may rise more than necessary. Therefore, it is desirable to cool the housing member and the holding member over time before performing the next vapor deposition process. If the housing member and the holding member are configured to be detachable and a plurality of the same shape are prepared, the housing member and the holding member used for one vapor deposition process are removed, and another housing member and the holding member are attached. Since the next deposition processing can be performed immediately, large-scale processing can be performed efficiently. Further, the longitudinal direction inside the housing member in the vapor deposition apparatus as described above is divided to form two or more housing partitions, and the processing is performed by storing the objects to be processed one by one or a small amount in each of the storage partitions. By this, it is possible to suppress the occurrence of cracks and chips in the workpiece due to the collision of the workpieces inside the housing member, and thus it is more effective to suppress the generation of protrusions due to damage to the workpiece. It is possible to perform it.

[0028]

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, for example, as described in U.S. Pat. No. 4,770,723 and U.S. Pat. , Nd ₁₄ Fe ₇₉ B ₆ Co obtained by performing surface processing
_The measurement was performed using a sintered magnet of _one composition having a diameter of 9 mm and a thickness of 3 mm (hereinafter, referred to as a magnet test piece).

Example 1: A cylindrical barrel having a diameter of 355 mm
× The vapor deposition device shown in FIG. 1 which is made of stainless steel having a length of 1200 mm and has an opening ratio of a mesh of 64% (aperture serving as an opening is a square having a side of 4 mm and a wire diameter of 1 mm). The following experiment was performed using the same configuration as the vapor deposition apparatus shown in FIG. 2). Shot blasting was performed on the magnet body test piece to remove an oxide layer on the surface of the test piece generated by the surface processing in the previous step. A test piece of the magnet body from which the oxide layer has been removed is placed in each of two cylindrical barrels.
A total of 10,000 pieces were stored in each of the 000 pieces. After evacuating the vacuum processing chamber to 1 × 10 ⁻³ Pa or less, while rotating the rotation shaft at 1.5 rpm, the Ar gas pressure was reduced to 1P.
a, Sputtering was performed for 20 minutes under the condition of a bias voltage of -500 V to clean the surface of the magnet test piece. continue,
Under the conditions of an Ar gas pressure of 1 Pa and a bias voltage of -100 V,
While replenishing an aluminum wire as a metal deposition material at a wire feed rate of 3 g / min, this was heated to evaporate and ionize, and an aluminum deposition coating was formed on the surface of the magnet test piece by an ion plating method for 20 minutes. After cooling, the following items were evaluated for the magnet test piece having an aluminum vapor-deposited coating. Temperature of magnet test piece at the end of vapor deposition (average value of n = 10) Vickers hardness of aluminum vapor-deposited film at end of vapor deposition (average value of n = 3) Film thickness of formed aluminum vapor-deposited film (n = 10)
(Appearance of individual magnet body test pieces) Number of magnet body test pieces in which one or more protrusions having a height exceeding 100 μm from the average line of the roughness curve in JIS B0601-1994 were generated (protrusion failure). number)
(N = 500) After projecting a projection material (glass beads manufactured by Shinto Breiter Co., Ltd., trade name: GB-AG) at a projection pressure of 0.2 MPa and performing a peening treatment, the temperature is 80 ° C. × 90% relative humidity.
The corrosion resistance test was performed under the condition of standing for 500 hours under high temperature and high humidity conditions, and the number of rusted magnet test pieces (the number of defective rusting) (n = 10) after the peening treatment under the above conditions The magnet body test piece was bonded to a cast iron jig using a cyanoacrylate resin-based adhesive (trade name: Loctite 406, manufactured by Henkel Japan Co., Ltd.), and after standing for 24 hours, the compressive shear strength was measured. Measurement (average value of n = 10) The measurement of the temperature of the magnet body test piece was not performed simultaneously with the formation of the vapor-deposited film evaluated in the above, but was separately performed under the same conditions as the conditions for forming the vapor-deposited film. . The specific method is
After shaving a plurality of thermo crayons (manufactured by NOF Engineering Co., Ltd.) indicating each indicated temperature, wrap the aluminum wrap in aluminum foil, wind it around a magnet test piece, perform vapor deposition, and then apply the thermo crayon corresponding to any temperature. A method was employed to confirm whether or not was melted. The Vickers hardness of the aluminum vapor-deposited film at the end of the vapor deposition was measured using a high-temperature micro-hardness tester QM manufactured by Nippon Kogaku Co., Ltd. as a measuring device, and the magnet test piece having the aluminum vapor-deposited film obtained by the above method. Was heated to the temperature at the end of vapor deposition, and measured under the conditions of a test load of 0.5 N and a load time of 30 seconds. In addition, the number of defective protrusions was determined by observing the appearance of the magnet test piece having the aluminum vapor-deposited film obtained by the above method using a magnifying glass (10 times) and confirming the presence of protrusions. The height of the largest protrusion was determined by using a scanning confocal laser microscope (OLS1100 manufactured by Olympus Optical Industrial Co., Ltd.) and determined. Table 1 shows the results.

Example 2 The following experiment was conducted using the vapor deposition apparatus shown in FIGS. Here, the cylindrical barrel is made of stainless steel having a diameter of 110 mm and a length of 600 mm, and has an opening ratio of a mesh of 64% (a square opening having a side of 4 mm and a wire diameter of 1 mm). One support member supports six (two in total, twelve). Shot blasting was performed on the magnet body test piece to remove an oxide layer on the surface of the test piece generated by the surface processing in the previous step. The magnet body specimen from which the oxide layer was removed was 1
Each of the two cylindrical barrels contained 850 pieces, two sets each on the left and right, for a total of 20400 pieces. Thereafter, an aluminum vapor-deposited film was formed on the surface of the magnet test piece by the ion plating method for 40 minutes in the same manner as in Example 1.
The same evaluation was performed. Table 1 shows the results.

Example 3 In Example 1, each of the two cylindrical barrels was prepared by removing 5 pieces of the magnet body specimen from which the oxide layer had been removed.
000 pieces each, a total of 10,000 pieces were accommodated, and a film thickness of 10
Instead of forming an aluminum vapor-deposited coating having a thickness of μm, each of the two cylindrical barrels contained 75,000 magnet test pieces from which the oxide layer had been removed, for a total of 15,000 magnet specimens, and were magnetized by ion plating for 30 minutes. An aluminum vapor-deposited film was formed on the surface of the body test piece (other conditions were the same as in Example 1), and the same evaluation as in Example 1 was performed. Table 1 shows the results.

Example 4 In Example 1, the magnet body test piece from which the oxide layer was removed in each of the two cylindrical barrels was 5
000 pieces each, a total of 10,000 pieces were accommodated, and a film thickness of 10
Instead of forming an aluminum deposited film having a thickness of μm, each of the two cylindrical barrels received 10,000 magnet body specimens from which the oxide layer had been removed, for a total of 20,000,
An aluminum vapor-deposited film was formed on the surface of the test piece of the magnet by the ion plating method for one minute.
The same evaluation as in Example 1 was performed. Table 1 shows the results
Shown in

COMPARATIVE EXAMPLE 1 In Example 4, a 10 μm-thick aluminum vapor-deposited film was formed on the surface of a magnet test piece by an ion plating method for 40 minutes while supplying an aluminum wire at a wire feed rate of 3 g / min. Instead, while depositing an aluminum wire at a wire feed rate of 1.5 g / min, an aluminum vapor-deposited film was formed on the surface of the magnet test piece by the ion plating method for 80 minutes (the other conditions were the same as in Example 4). The same evaluation as in Example 1 was performed. Table 1 shows the results.

[0034]

[Table 1]

As is clear from Table 1, in Examples 1 to 4, the temperature of the magnet test piece was set to not more than ／ of the melting point (Tm) (° C.) of the bulk aluminum, that is, 44.
Since the Vickers hardness of the coating formed on the surface of the magnet test piece was maintained at 25 or more by performing deposition while maintaining the temperature at 0 ° C. or less, it is possible to effectively suppress the generation of protrusions in the coating. (For example, in Example 1, there was a projection, but the maximum height was about 30 μm),
Excellent adhesive strength was obtained even with the adhesive.
Further, damage to the coating itself was suppressed, and the formed coating was excellent in appearance and corrosion resistance. On the other hand, in Comparative Example 1, since the coating was formed with a deposition time twice as long as the deposition time in Example 4, the magnet body test piece was heated more than necessary for a longer time, and the temperature was 440 ° C.
Has been exceeded. As a result, the Vickers hardness of the coating formed on the surface of the magnet test piece becomes smaller than 25, and the coating becomes soft and easily damaged, and as a result, 1
Many projections having a height exceeding 00 μm were formed. Even when an attempt was made to bond the magnet body test piece with the protrusions to the cast iron jig using an adhesive, the adhesive did not sufficiently cure under ordinary bonding conditions, and excellent adhesive strength could not be obtained. In addition, the coating itself was damaged, and the appearance and corrosion resistance were not satisfactory.

Example 5: The cylindrical barrel has a diameter of 355 mm
× using a deposition film forming apparatus shown in FIG. 1, which is made of stainless steel having a length of 1200 mm and has an opening ratio of a mesh of 64% (aperture serving as an opening is a square having a side of 4 mm and a wire diameter of 1 mm). The following experiment was performed. Shot blasting was performed on the magnet body test piece to remove an oxide layer on the surface of the test piece generated by the surface processing in the previous step. The magnet specimen from which the oxide layer has been removed is placed on one of the two cylindrical barrels.
000 were accommodated. After evacuating the vacuum processing chamber to 1 × 10 ⁻³ Pa or less, while rotating the rotation shaft at 1.5 rpm, the Ar gas pressure is 1 Pa and the bias voltage is −50.
The magnet body test piece surface was cleaned by sputtering for 20 minutes under the condition of 0V. Subsequently, a zinc vapor deposition film was formed on the surface of the test piece of the magnet by a vacuum vapor deposition method using an electron beam heating method, using a zinc ingot as a metal vapor deposition material under the condition of an Ar gas pressure of 0.1 Pa. In addition, the vapor deposition was performed for four hours, in which the operation of stopping the heating of the ingot every 15 minutes, leaving it to stand for 10 minutes, and then restarting the heating was repeated four times, while suppressing the temperature rise of the magnet. After allowing to cool, the following items were evaluated for the magnet test piece having the zinc deposited film. Temperature of magnet test piece at end of vapor deposition (average value of n = 10) Vickers hardness of zinc deposited film at end of vapor deposition (n =
(Average value of 3) Thickness of formed zinc vapor-deposited film (average value of n = 10) Appearance of each test piece of magnet body Projection having a height exceeding 100 μm from the average line of the roughness curve in JIS B0601-1994 Number of magnet body test pieces where one or more were generated (number of defective protrusions)
(N = 500) The measurement of the temperature of the magnet body test piece was not performed simultaneously with the formation of the vapor-deposited film evaluated in the above, but was separately performed under the same conditions as the conditions for forming the vapor-deposited film. The specific method is
After shaving a plurality of thermo-crayons (manufactured by NOF Engineering Co., Ltd.) indicating the indicated temperatures, wrap them in a zinc foil, wind them around a magnet test piece and perform evaporation, and then apply the thermo-crayon corresponding to any temperature A method was employed to check whether or not was melted. The Vickers hardness of the deposited zinc film at the end of the vapor deposition was measured by the same method as described in Example 1. The number of defective protrusions was determined and determined by the same method as that described in Example 1. Table 2 shows the results.

Comparative Example 2: Stop heating in Example 5 →
Continuously, without performing the operation of leaving → heating again
The ingot was heated for a period of time to perform vapor deposition, and a zinc vapor-deposited film was formed on the surface of the test piece of the magnet body. Table 2 shows the results.

[0038]

[Table 2]

As is clear from Table 2, when a zinc vapor-deposited film is formed on the surface of the magnet test piece, the temperature of the magnet test piece is set to 2 / (the melting point (Tm) (° C.)) of the bulk zinc.
3 or less, that is, by performing deposition while maintaining at 280 ° C. or less, since the Vickers hardness of the coating formed on the surface of the magnet test piece was maintained at 25 or more, there was no generation of protrusions in the coating, The coating itself was also excellent in appearance.
On the other hand, when the temperature of the magnet body test piece exceeds 280 ° C., a large number of protrusions having a height of more than 100 μm are formed on the coating, and the coating itself is damaged, which is not satisfactory in appearance and corrosion resistance. Was.

[0040]

According to the present invention, a vapor deposition apparatus having a vapor deposition material evaporation section and a storage member or holding member for storing or holding an object to be processed is provided in a vacuum processing chamber. While depositing the metal deposition material on the surface of the workpiece while rotating the holding member about the horizontal rotation axis, the Vickers hardness of the coating formed on the surface of the workpiece is maintained at 25 or more. By performing, the metal deposition film formed on the surface of the object to be processed is softened, the collision or rubbing between the objects to be processed, the collision or rubbing between the object to be processed and the barrel wall surface causes the formed film to be formed. It is possible to suppress the possibility of being easily damaged, and as a result, it is possible to effectively suppress the formation of projections on the coating. When a metal coating film is formed on the surface of the object to be processed and subsequently a ceramic coating film such as Al ₂ O ₃ or TiN is formed on the surface, if a protrusion is generated in the metal coating film,
This will affect the adhesion reliability and dimensional accuracy of the subsequently formed ceramic coating with the adhesive, but the present invention can also avoid such adverse effects.

[Brief description of the drawings]

FIG. 1 is a schematic front view (partially transparent view) of the inside of a vacuum processing chamber of an example of a vapor deposition apparatus applied to the present invention.

FIG. 2 is a schematic front view (partially transparent view) of the inside of a vacuum processing chamber of another example of the vapor deposition apparatus applied to the present invention.

FIG. 3 is a schematic perspective view of a cylindrical barrel supported by the support member.

FIG. 4 is a schematic front view (partially transparent view) of the inside of a vacuum processing chamber of still another example of the vapor deposition apparatus applied to the present invention.

FIG. 5 is a schematic perspective view of a cylindrical barrel whose inside is divided.

FIG. 6 is a schematic perspective view of a jig used in still another example of the vapor deposition apparatus applied to the present invention.

[Explanation of symbols]

 1, 51, 101 Vacuum processing chamber 2, 52, 102 Boat (evaporator) 5, 55, 105 Cylindrical barrel 6, 56, 106, 156 Rotating shaft 57, 157 Supporting member 58 Supporting shaft 59, 109 Aluminum wire 30, 80, 130 Rare earth permanent magnet 160 Holding member (hanging member) 190 Ring magnet

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshimi Tochishita 1062 Oyabu, Yabu-cho, Yabu-gun, Hyogo Kinki-Sumi Toku Denshi Co., Ltd. F-term (reference) 4K029 AA02 AA22 BA03 BA18 CA03 CA17 DA01 EA08

Claims (15)

[Claims] 1. A vacuum processing chamber, wherein:
Using a vapor deposition apparatus provided with a housing member and / or a holding member for housing and / or holding an object to be processed, while rotating the housing member and / or the holding member around a horizontal rotation axis, the metal When depositing a deposition material on the surface of the object to be processed, suppressing the formation of protrusions in the metal vapor-deposited film characterized by performing the evaporation while maintaining the Vickers hardness of the film formed on the surface of the object to be processed at 25 or more. Method. 2. The temperature of an object to be processed housed and / or held in the housing member and / or the holding member is maintained at 2/3 or less of the melting point (Tm) (° C.) of the bulk of the metal deposition material. 2. The method according to claim 1, wherein the Vickers hardness of the coating formed on the surface of the workpiece is maintained at 25 or more. 3. The method according to claim 2, wherein the metal deposition material is aluminum, and the deposition is performed while maintaining the temperature of the object to be processed at 350 ° C. or lower. 4. The method according to claim 2, wherein the metal deposition material is zinc, and the deposition is performed while maintaining the temperature of the object to be processed at 250 ° C. or lower. 5. The method according to claim 1, wherein the vapor deposition is performed by a vacuum vapor deposition method or an ion plating method.
The method according to any of the above. 6. The method according to claim 1, wherein the housing member and / or the holding member are configured to be detachable. 7. The method according to claim 1, wherein the housing member is a cylindrical barrel formed of a mesh. 8. The cylindrical barrel is rotatably supported around a rotation axis of a support member that is rotatable about a horizontal rotation axis, and is revolvably supported by rotating the support member. 8. The method according to claim 7, wherein the support member revolves around an axis of rotation. 9. The method according to claim 8, wherein the cylindrical barrel and / or a support member for supporting the cylindrical barrel are detachably configured. 10. The method according to claim 8, wherein a plurality of the cylindrical barrels are annularly supported outward in the circumferential direction of the rotation axis of the support member. 11. The inside of the cylindrical barrel is divided into two parts.
8. The method according to claim 7, wherein said receiving portion is formed. 12. The method according to claim 11, wherein the inside of the cylindrical barrel is radially divided from an axis of rotation to form two or more receiving portions. 13. The method according to claim 1, wherein the object to be processed is a rare earth permanent magnet. 14. A rare earth permanent magnet having a metal deposited film in which the formation of projections is suppressed by the method according to claim 13. 15. The rare-earth permanent magnet according to claim 14, wherein the height of the projections present in the metal deposition film is 100 μm or less from the average line of the roughness curve in JIS B0601-1994.