JP5381577B2 - Method for producing corrosion-resistant R—Fe—B sintered magnet - Google Patents

Description

  The present invention relates to a method for producing an R—Fe—B sintered magnet exhibiting excellent corrosion resistance.

R-Fe-B based sintered magnets typified by Nd-Fe-B based sintered magnets have high magnetic properties and are used in various fields today. However, since the R—Fe—B based sintered magnet contains a highly reactive rare earth element: R, it is easily oxidized and corroded in the atmosphere, and when used without any surface treatment, a slight amount of acid is present. Corrosion progresses from the surface due to the presence of alkali, moisture, and the like, and rust is generated, which causes deterioration and variation in magnet characteristics. Furthermore, when a magnet in which rust is generated is incorporated in an apparatus such as a magnetic circuit, the rust may be scattered to contaminate peripheral components.
In view of the above points, for the purpose of imparting excellent corrosion resistance to the R—Fe—B based sintered magnet, an Al film is formed on the surface by vapor phase plating such as vapor deposition. Yes. In addition to being excellent in corrosion resistance, the Al coating has excellent adhesion reliability with the adhesive required when assembling the parts (the coating film and adhesive are required to reach the breaking strength inherent in the adhesive). Therefore, the R-Fe-B sintered magnet having an Al coating on the surface is widely applied to R-Fe-B sintered magnets that require strong adhesive strength. Used in various motors.

Among various types of motors, R-Fe-B sintered magnets incorporated in motors for automobiles are used in the environment where the temperature changes in the environment of use, and in cold regions, the chlorine ions contained in the antifreeze sprayed on the roads. It can be said to be the magnet in the harshest usage environment because it is exposed to salt water near the coast. Therefore, the R—Fe—B based sintered magnet incorporated in the motor for automobiles is required to exhibit particularly excellent corrosion resistance. Therefore, various methods for improving the corrosion resistance of the Al coating have been proposed. For example, Patent Document 1 discloses a method for improving the film quality of the Al coating by including 1 ppm to 20 ppm of hydrogen in the Al coating. Have been described.
However, even if such a method is adopted, it must be said that it is difficult to completely prevent corrosion of the R—Fe—B based sintered magnet. One of the reasons is that the crystal structure constituting the deposited Al film is a columnar structure (for example, Patent Document 2). This crystal structure is a columnar structure that grows in the thickness direction of the film, and there are fine voids between the crystals, so that moisture etc. reaches the surface of the magnet body from the film surface through these voids. Causes corrosion. In order to prevent such a phenomenon, as described in Patent Document 1, it is effective to smooth the surface of the film and seal the gap by performing a peening process on the Al film. Nevertheless, corrosion of the magnet occurs under severe use environment.

JP 2001-32062 A Japanese Patent Laying-Open No. 2005-191276

  Therefore, an object of the present invention is to provide a method for producing an R—Fe—B based sintered magnet that exhibits excellent corrosion resistance even under severe conditions.

  As a result of intensive studies in view of the above points, the inventors of the present invention conducted a peening treatment on an Al coating containing a larger amount of hydrogen than the amount proposed in Patent Document 1, and the coating surface In addition to smoothing the pores and gaps in the gap, the crystal structure of the film itself is modified, and at least part of the columnar structure grown in the thickness direction of the film is randomly destroyed. It has been found that the corrosion resistance of the Al coating is improved by changing the structure.

The manufacturing method of the corrosion-resistant R—Fe—B based sintered magnet of the present invention based on the above knowledge has a hydrogen content on the surface of the R—Fe—B based sintered magnet as described in claim 1. After vapor-depositing a film composed of 50 ppm or more of Al or an alloy thereof, peening treatment is performed on the vapor-deposited film composed of Al or an alloy thereof of 50 ° C. or higher, thereby forming a crystal structure of at least a part of the film. It is characterized by being modified into a structure having no voids between crystals .
The manufacturing method according to claim 2 is characterized in that, in the manufacturing method according to claim 1, the film formation rate of the film made of Al or an alloy thereof is set to 0.10 μm / min to 10 μm / min .
Also, corrosion resistance R-Fe-B sintered magnets of the present invention, as claimed in claim 3, characterized by comprising manufactured by the manufacturing method according to claim 1 or 2 wherein.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the R-Fe-B type sintered magnet which exhibits the outstanding corrosion resistance also under severe conditions can be provided.

Typical front view inside vacuum processing chamber of one embodiment of vapor deposition film forming apparatus suitable for manufacturing R-Fe-B based sintered magnet having film made of Al or its alloy on the surface (partially see through) Figure). FIG. 6 is a cross-sectional photograph taken by a transmission electron microscope inside the Al coating formed on the surface of the magnet specimen in Example 5 (near the center in the thickness direction of the coating) and a crystal diffraction image of a portion indicated by a circle in the figure. . It is the crystal diffraction image of the part shown with the cross-sectional photograph by the transmission electron microscope inside the Al film formed in the surface of the magnet body test piece in Comparative Example 1 (near the center part in the thickness direction of the film) and a circle in the figure. .

1 Vacuum processing chamber 2 Boat (evaporation part)
DESCRIPTION OF SYMBOLS 3 Support table 4 Boat support stand 5 Cylindrical barrel 6 Rotating shaft 7 Support member 8 Support shaft 9 Wire of vapor deposition material 10 Feeding reel 11 Heat-resistant protective tube 12 Notch window 13 Feeding gear 30 Workpiece

  The method for producing a corrosion-resistant R—Fe—B based sintered magnet according to the present invention is a method in which a film made of Al or an alloy thereof having a hydrogen content of 50 ppm or more is deposited on the surface of an R—Fe—B based sintered magnet. A peening treatment is performed on a coating film made of deposited Al or an alloy thereof.

  In the present invention, the deposition of a coating made of Al or an alloy thereof on the surface of the R—Fe—B sintered magnet in the present invention is performed, for example, by supplying a deposition source of Al or an alloy thereof to the evaporation portion of the deposition material by a wire feed system. For example, a vapor deposition film forming apparatus in which evaporation of a vapor deposition source of Al or an alloy thereof in a vaporization section is performed by a resistance heating method is described in JP-A-2001-335921. A vapor deposition film forming apparatus comprising a vapor deposition material evaporation section and a cylindrical barrel formed of a mesh for accommodating an object to be vapor-deposited on the surface of the vapor deposition film, and having a horizontal rotation axis A cylindrical barrel is supported to be revolved outwardly in the circumferential direction of the rotation axis of the support member that is rotatable about the center, and revolves around the rotation axis of the support member by rotating the support member. A vapor deposition film can be formed on the surface of the object to be processed by evaporating while continuously supplying the wire-shaped vapor deposition material to the heated evaporation section while making the distance between the moving barrel barrel and the evaporation section variable. It can implement easily by using a vapor deposition film forming apparatus.

  FIG. 1 is a schematic front view (partially perspective view) of the inside of a vacuum processing chamber of one embodiment of the vapor deposition film forming apparatus described in JP-A-2001-335921. Two support members 7 that are rotatable around a rotation shaft 6 on a horizontal rotation axis are provided above the inside of the vacuum processing chamber 1 connected to a vacuum exhaust system (not shown). A cylindrical barrel 5 formed of six stainless steel mesh wire nets is supported in an annular manner by a support shaft 8 so as to revolve on the outer side in the circumferential direction of the rotary shaft 6. A plurality of boats 2, which are evaporating portions for evaporating the vapor deposition material, are arranged on a boat support base 4 erected on a support table 3 below the vacuum processing chamber 1. Inside the support table 3, a wire 9 made of vapor deposition material is wound and held on a supply reel 10. The tip of the wire 9 of vapor deposition material is guided above the boat 2 by a heat-resistant protective tube 11 facing the inner surface of the boat 2. A cutout window 12 is provided in a part of the protective tube 11, and a feeding gear 13 provided corresponding to the cutout window 12 is in direct contact with the vapor deposition material wire 9, so that the vapor deposition material wire 9 is connected. By being drawn out, the vapor deposition material is constantly supplied into the boat 2, and the film formation rate of the vapor deposition film can be freely controlled by adjusting the feed rate of the wire 9 of the vapor deposition material. When the support member 7 is rotated around the rotation shaft 6 (see the arrow in FIG. 1), the cylindrical barrel 5 supported by the support shaft 8 on the outer side of the rotation shaft 6 of the support member 7 in the circumferential direction is In response to this, a revolving motion is performed around the rotating shaft 6. As a result, the distance between the individual cylindrical barrels and the evaporating part disposed below the support member varies, and the following effects are exhibited. That is, the cylindrical barrel located at the lower part of the support member 7 is close to the evaporation part. Therefore, a vapor deposition film is efficiently formed on the surface of the workpiece 30 accommodated in the cylindrical barrel. On the other hand, the object to be processed accommodated in the cylindrical barrel away from the evaporator is released from the heating state and cooled by the distance away from the evaporator. Therefore, softening of the vapor deposition film formed on the surface is suppressed during this time. Thus, if this vapor deposition film forming apparatus is used, it becomes possible to achieve efficient formation of a vapor deposition film and suppression of softening of the formed vapor deposition film simultaneously.

  The vapor deposition formation of a film made of Al or an alloy thereof having a hydrogen content of 50 ppm or more is, for example, supplying a wire-like vapor deposition material having a hydrogen content of 3 ppm to 10 ppm to the boat at a feed rate of 1 g / min to 15 g / min, The film can be formed at a film forming speed of 0.10 μm / min to 10 μm / min (the film forming speed varies depending on the wire feeding speed, magnet throughput, etc., but is generally within this speed range. The target film can be formed by vapor deposition). If the wire-like vapor deposition material has too little hydrogen content, or if the wire-like vapor deposition material feed rate or the film formation rate is too slow, the hydrogen content in the film may not exceed 50 ppm. . In order to effectively perform the peening treatment on the coating film in the subsequent step, the hydrogen content in the coating film is desirably 100 ppm or more, and more desirably 130 ppm or more. The upper limit of the hydrogen content in the film is not particularly limited, but when the film is deposited under the above conditions, the maximum amount of hydrogen that can be included in the film is approximately 200 ppm. The temperature of the boat is controlled to 1300 ° C to 1500 ° C in order to prevent the molten deposition material in the boat from overflowing and hydrogen from boiling and causing splash, and to stably deposit the coating. It is desirable to do. In order to improve the film thickness uniformity of the coating, a stirring medium may be accommodated in the cylindrical barrel. Examples of the stirring medium include ceramic balls having an average particle diameter of 5 mm to 15 mm.

Note that in the above-described method using a vapor deposition material containing hydrogen, hydrogen can be supplied into the processing chamber when the vapor deposition material is evaporated. However, even if the processing chamber is in a reducing atmosphere, for example, even under an oxygen partial pressure of 10 ⁻³ Pa or higher, oxidation of the deposited material at the melted or evaporated stage is prevented, and the deposition of the film is stabilized. It is convenient in that it can be performed.

  Next, a peening treatment is performed on the coating film made of Al or an alloy thereof having a hydrogen content of 50 ppm or more deposited on the surface of the R—Fe—B sintered magnet by the above method. As described above, the crystal structure constituting the deposited Al (or alloy thereof) film is a columnar structure grown in the thickness direction of the film, but surprisingly, the hydrogen content in the film is very small. When it is 50 ppm or more, by performing a peening treatment on the film, the crystal structure itself of the film is modified, and at least a part of the columnar structure is randomly broken to form a dense structure having no voids between crystals. By changing, the corrosion resistance of the coating is improved. In order to increase the degree of modification of the crystal structure of the film and enjoy this effect more reliably, as described above, the hydrogen content in the film is preferably 100 ppm or more, more preferably 130 ppm or more. The film thickness is preferably 3 μm or more. This is because if the film thickness is less than 3 μm, the effect of imparting corrosion resistance to the magnet may not be obtained. The film thickness is preferably 50 μm or less. This is because even if the film thickness is increased, the effect of imparting corrosion resistance to the magnet does not change, and only the production cost increases.

  The peening treatment for the coating is performed using, for example, glass beads or steel balls having an average particle diameter of 80 μm to 200 μm (preferably 100 μm to 150 μm) and a Mohs hardness of 3 to 8 as a projection material, and 0.01 MPa to 0.5 MPa. What is necessary is just to perform about 1 minute-1 hour with respect to a film by the projection pressure of. If the peening treatment is insufficient, the crystal structure of the film may not be sufficiently modified. On the other hand, if it is excessive, the film may be peeled off from the magnet surface. The apparatus used for the peening process is not particularly limited as long as it can project the projection material from the projection nozzle onto the magnet. For example, a blasting apparatus described in JP-A-2001-34175 Can be preferably used. The distance between the projection nozzle and the magnet is desirably 80 mm to 150 mm. In addition, it is desirable to perform a peening process with respect to the film of 50 degreeC or more. This is because a film having a temperature of 50 ° C. or higher has a Vickers hardness of 50 or less and is in a softer state than at room temperature, so that the crystal structure of the film can be modified more effectively. The coating temperature is more preferably 100 ° C. or higher. In order to perform a peening process on a film having a temperature of 50 ° C. or higher, it is desirable to perform the process within 30 minutes after the film formation is completed (for example, when the cooling operation is performed by opening the film to the atmosphere immediately after the film formation is completed).

  By peening a coating with a hydrogen content of 50 ppm or more, not only the coating surface is smoothed and voids are sealed, but the crystal structure of the coating itself is modified, and the columnar shape grows in the thickness direction of the coating. Corrosion resistance of the coating is improved by changing to a dense structure having no voids between crystals in which at least a part of the structure is randomly broken. The modification of the crystal structure of the film may be performed at least in a part thereof, but it is desirable to be performed over the entire film. In addition, it is desirable that at least a part of the tissue after the modification has an equiaxially refined structure. The shape of the structure which is refined equiaxed is, for example, 0.1 <((a) where the length of the crystal structure in the film is a in any direction and b is the length perpendicular to the direction. b / a) is a shape that satisfies the mathematical formula of <2, and both a and b are, for example, 0.1 μm to 3 μm.

  In addition, when the film vapor-deposited and formed on the surface of the R—Fe—B based sintered magnet is a film made of an Al alloy, the content of metal components other than Al is desirably 10 wt% or less. For example, an Al alloy coating containing 3 wt% to 7 wt% of Mg as a metal component other than Al is desirable in that it has excellent salt water resistance. The coating film made of Al or an alloy thereof may contain a trace component that cannot be avoided.

  The rare earth element (R) in the R—Fe—B based sintered magnet used in the present invention may contain at least one of Nd, Pr, Dy, Ho, Tb, and Sm, and further La, Ce. , Gd, Er, Eu, Tm, Yb, Lu, Y may be included. Usually, one type of R is sufficient, but in practice, a mixture of two or more types (such as misch metal and didymium) can also be used for reasons of convenience. If the content of R in the R—Fe—B based sintered magnet is less than 10 atomic%, the α-Fe phase precipitates, so that high magnetic properties, particularly high coercive force (iHc) cannot be obtained. If it exceeds atomic%, the R-rich non-magnetic phase increases and the residual magnetic flux density (Br) decreases, and a permanent magnet having excellent characteristics cannot be obtained. Therefore, the R content is 10 atomic% to 30 atomic% of the composition. It is desirable that

  If the Fe content is less than 65 atomic%, Br decreases, and if it exceeds 80 atomic%, high iHc cannot be obtained. Therefore, the content of 65 atomic% to 80 atomic% is desirable. Further, by substituting a part of Fe with Co, the temperature characteristics can be improved without impairing the magnetic characteristics of the obtained magnet. However, if the Co substitution amount exceeds 20 atomic%, the magnetic characteristics will be improved. Is undesirable as it degrades. When the amount of Co substitution is 5 atom% to 15 atom%, Br increases as compared with the case where it is not substituted, and thus it is desirable for obtaining a high magnetic flux density.

  When the content of B is less than 2 atomic%, the rhombohedral structure becomes the main phase, and high iHc cannot be obtained. When it exceeds 28 atomic%, the B-rich nonmagnetic phase increases, and the Br decreases. Since a permanent magnet having the characteristics cannot be obtained, the content is preferably 2 atomic% to 28 atomic%. Moreover, in order to improve the manufacturability and reduce the price of the magnet, at least one of 2.0 wt% or less P and 2.0 wt% or less S is contained in a total amount of 2.0 wt% or less. May be. Furthermore, the corrosion resistance of the magnet can be improved by replacing a part of B with C of 30 wt% or less.

  Furthermore, at least one of Al, Ti, V, Cr, Mn, Bi, Nb, Ta, Mo, W, Sb, Ge, Sn, Zr, Ni, Si, Zn, Hf, and Ga is added. It is effective in improving the squareness of the demagnetization curve, improving manufacturability, and reducing the price. It should be noted that the amount of Br added is preferably within a range satisfying the condition because Br needs to be at least 9 kG in order to make the maximum energy product (BH) max 20 MGOe or more. The R—Fe—B sintered magnet may contain impurities inevitable in industrial production in addition to R, Fe, and B.

  Further, among the R—Fe—B sintered magnets used in the present invention, a compound having a tetragonal crystal structure having an average crystal grain size in the range of 1 μm to 80 μm is a main phase, and the volume ratio is 1 What is characterized by including a non-magnetic phase (excluding the oxide phase) of 50% to 50% shows iHc ≧ 1 kOe, Br> 4 kG, (BH) max ≧ 10 MGOe, and the maximum value of (BH) max is Reach over 25 MGOe.

  Further, another corrosion-resistant film may be laminated on the surface of the film made of Al or its alloy after the peening treatment. By adopting such a configuration, the characteristics of the coating made of Al or an alloy thereof in which at least a part of the crystal structure is modified by peening treatment are enhanced or supplemented, and further functionality is imparted. Can be.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is limited to the following description and is not interpreted. In the following examples and comparative examples, for example, as described in U.S. Pat. No. 4,770,723 and U.S. Pat. No. 4,792,368, a known cast ingot is roughly pulverized, and after fine pulverization, molding, sintering, Using a sintered magnet (hereinafter referred to as a magnet specimen) having a length of 50 mm, a width of 20 mm, and a width of 2 mm of Nd ₁₄ Fe ₇₉ B ₆ Co ₁ composition (at%) obtained by heat treatment and surface treatment. I went.

Example A:
(Step 1) Vapor deposition of Al coating on the surface of the magnet test piece The following procedure was performed using the vapor deposition coating forming apparatus shown in FIG. The twelve cylindrical barrels arranged in the vacuum processing chamber have a diameter of 110 mm × length of 600 mm, a stainless steel mesh wire mesh (opening ratio: about 80%, opening shape: square with a side of 10 mm, line width: 2 mm) was used.
The magnetic body test piece was subjected to sand blasting to remove the oxide layer on the surface of the test piece generated by the surface processing in the previous step. Forty-five magnet test specimens from which the oxide layer has been removed are accommodated in each cylindrical barrel, and ceramic balls having an average particle diameter of 10 mm (manufactured by Shinto Kogyo Co., Ltd.) are accommodated as a stirring medium. After evacuating the process chamber to a total pressure of 4 × 10 ⁻² Pa, Ar gas was introduced so that the total pressure was 5 Pa, and then the bias was applied while rotating the rotating shaft of the barrel at 4.5 rpm. Under the condition of a voltage of −1.0 kV, glow discharge was performed for 15 minutes to clean the surface of the magnet specimen.
Subsequently, under the conditions of Ar gas pressure 1.3 Pa and bias voltage −0.5 kV, while rotating the rotating shaft of the barrel at 4.5 rpm, the hydrogen content of Al wire (conforming to JIS A1070) was 5 ppm. The feeding speed was adjusted to continuously supply the Al wire to the evaporation section, which was heated and evaporated to be ionized, ion-plated, and an Al film was deposited on the surface of the magnet specimen. Table 1 shows the details of the film formation conditions and the film formation results. In addition, the film thickness of the film was calculated | required as an average value of ten magnet body test pieces. The film formation rate was determined by dividing the film thickness by the deposition time. The hydrogen content of the coating was measured by a dissolution method from coatings deposited on three glass plates fixed on the outside of the cylindrical barrel, and the average value was obtained.

(Step 2) Peening treatment for Al coating deposited on the surface of the magnet test piece Shot peening using glass beads having a Mohs hardness of 6 and an average particle size of 120 μm (manufactured by Kyoei Abrasives) under the conditions shown in Table 2 went.

  Using a constant temperature and humidity tester (LH-112: manufactured by Tabay Espec Co., Ltd.), a temperature of 80 ° C. relative to the magnet body test piece having the Al vapor-deposited film subjected to shot peening on the surface obtained as described above. A wet test was performed by exposing to a humid atmosphere of 90% humidity. After exposing the test sample to a humid atmosphere for 1000 hours, confirm the presence or absence of rust, take a picture, calculate the rust area ratio of the coating surface by image processing, and the rust area ratio is 1% or less A case of exceeding 1% was evaluated as defective. The results are shown in Table 3 (average value of two magnet body test pieces).

As is apparent from Tables 1 to 3, the hydrogen content of the Al coating deposited on the surface of the magnet specimen is determined by the amount of hydrogen released per unit time correlated with the feeding speed of the Al wire and the film formation rate. In addition to an increase in the amount of hydrogen released per unit time from the Al wire, the hydrogen partial pressure in the vacuum processing chamber at the time of vapor deposition formation increased, and also increased due to an increase in film formation rate. In addition, the effect of the peening treatment on the Al film was higher as the hydrogen content of the Al film was higher, and an excellent result was obtained in the evaluation based on the rust area ratio.
The crystal structure inside the Al coating formed on the surface of the magnet specimen in Example 5 (near the center in the thickness direction of the coating) and the Al coating formed on the surface of the magnet specimen in Comparative Example 1 The internal crystal structure (near the center in the thickness direction of the film) was analyzed by a cross-sectional photograph and a crystal diffraction image of the film with a transmission electron microscope. The results are shown in FIGS. 2 and 3, respectively. As is clear from FIG. 3, the latter crystal structure remains a columnar structure grown in the thickness direction of the film before shot peening, and there are fine voids between the crystals. On the other hand, as is clear from FIG. 2, the former crystal structure is a columnar structure before shot peening is changed into a dense structure having no voids between randomly broken crystals, etc. The presence of the axially refined tissue could be confirmed (the portion surrounded by a frame in FIG. 2. Both a and b were about 0.5 μm and b / a was about 1). The modification of the crystal structure observed in Example 5 was similarly recognized in other examples. Moreover, there was almost no change in the film thickness of the Al coating film due to shot peening in both the example and the comparative example.

Example B:
Example A and Example A except that instead of an Al wire having a hydrogen content of 5 ppm, an Al alloy wire having a hydrogen content of 7 ppm and containing 4.8 wt% of Mg (conforming to JIS A5356-WY) is used. When the same experiment was conducted, the same result as in Example A was obtained although there was a difference in degree.

  The present invention has industrial applicability in that it can provide a method for producing an R—Fe—B sintered magnet exhibiting excellent corrosion resistance even under severe conditions.

Claims (3)

On the surface of R-Fe-B based sintered magnet, after the hydrogen content was vapor deposited a coating of 50ppm or more Al or alloys thereof, with respect to coating of 50 ° C. or more Al or its alloy is deposited formed A method for producing a corrosion-resistant R—Fe—B based sintered magnet, wherein the peening treatment is performed to modify at least a part of the crystal structure of the coating into a structure having no voids between crystals . 2. The production method according to claim 1, wherein the film forming rate of the film made of Al or an alloy thereof is set to 0.10 [mu] m / min to 10 [mu] m / min . A corrosion-resistant R-Fe-B sintered magnet produced by the production method according to claim 1 or 2 .