Patent Grant
11232890
The present invention relates to an RFeB sintered magnet containing a rare-earth element (hereinafter referred to as “R”), iron (Fe) and boron (B) as main constituting elements.
RFeB sintered magnets were discovered in 1982 by Masato Sagawa et al. and have excellent characteristics that most of their magnetic characteristics such as residual magnetic flux density are far higher than those of conventional permanent magnets. Therefore, RFeB sintered magnets have been used in a variety of products, for example, various motors such as motors for automobiles such as hybrid automobiles and electric automobiles and motors for industrial machines, speakers, headphones, and magnetic resonance diagnostic devices using permanent magnet.
Earlier versions of the RFeB sintered magnet had a defect that the coercivity iHc is comparatively low among various magnetic characteristics. Later studies have revealed that the presence of a heavy rare-earth element RH such as Dy or Tb inside the RFeB sintered magnet improves the coercivity. The coercivity is a measure of the ability to withstand an external magnetic field without inverting magnetization when the external magnetic field opposite to the direction of magnetization is applied to the magnet. It is considered that the heavy rare-earth element RH has an effect of increasing the coercivity through an inhibition of the magnetization inversion. However, since the heavy rare-earth element RH is expensive and rare and also causes lowering of the residual magnetic flux density, it is not desirable to increase the content of the heavy rare-earth element RH.
Patent Literature 1 describes the addition of Ga (gallium) in order to improve the coercivity of the RFeB sintered magnet without adding the heavy rare-earth element RH. In general, in the RFeB sintered magnet, in the case where a ferromagnetic body having a large saturation magnetization is present in a crystal grain boundary, a magnetic interaction is generated among adjacent crystal grains. Therefore, when a reverse magnetic field (magnetic field whose direction is opposite to that of magnetization) is applied, and when the magnetization is inverted in a certain crystal grain, the magnetization of adjacent crystal grains is also inverted by such an interaction so that the coercivity is decreased. As such a ferromagnetic body having a large saturation magnetization, typical examples include one composed of R and Fe which have not been contained in the crystal grains. Contrarily, in the case where Ga (gallium) is added to the RFeB sintered magnet, a ferromagnetic body having a relatively small saturation magnetization, represented by R6Fe13Ga, is formed in the crystal grain boundary and the formation of a ferromagnetic body having a larger saturation magnetization is suppressed. Thereby, even when a reverse magnetic field is applied and magnetization is inverted at a certain crystal grain, the magnetic interaction that may invert the magnetization of adjacent crystal grains becomes weak, so that the coercivity is improved.
Patent Literature 1: JP-A 2014-132628
Patent Literature 2: WO 2014/017249
However, since Ga is also expensive, there occurs a problem that production costs increase in the case where Ga is added to the RFeB sintered magnet as described in Patent Literature 1.
An object of the present invention is to provide an RFeB sintered magnet having a high coercivity without using a heavy rare-earth element RH and Ga that are expensive additive elements as far as possible.
The RFeB sintered magnet according to the present invention, which is devised for solving the above problems, contains:
contains an RFeAl phase having an R6Fe14-xAlx structure in a crystal grain boundary, and
has a coercivity of 16 kOe or more.
The RFeAl phase having an R6Fe14-xAlx structure has a tetragonal crystal structure where the value of x may be a value ranging from 0.5 to 3.5. Moreover, a part of Fe of the RFeAl phase may be replaced by Co and also, as mentioned later, a part of Al of the RFeAl phase may be replaced by Cu in the case where the RFeB sintered magnet according to the present invention contains Cu. Furthermore, the ratio (molar ratio) of the number of R to the total number of atoms of Fe (Co) and Al (Cu) may slightly deviate from 6:14 owing to the generation of lattice defects.
As the rare-earth element R, a light rare-earth element such as Nd or Pr can be suitably used. Moreover, it is not necessary to use a heavy rare-earth element RH as the rare-earth element R. However, containing a heavy rare-earth element RH as a part of the rare-earth element R is not excluded from the present invention. That is, the present invention may contain a heavy rare-earth element RH as a part of the rare-earth element R.
The RFeB sintered magnet of the present invention may contain 0.2% by mass or less of Ga as an unavoidable impurity (not as an additive element) in addition to the above-described elements. Also, the RFeB sintered magnet of the present invention may contain 0.1% by mass or less of Cr (chromium), 0.1% by mass or less of Mn (manganese), 0.1% by mass or less of Ni (nickel), 2,000 ppm or less of N (nitrogen), and 2,000 ppm or less of C (carbon), as unavoidable impurities. It is desirable that the content of N is 1,000 ppm or less and the content of C is 1,000 ppm or less.
The RFeB sintered magnet according to the present invention can be produced through the following steps:
a step of preparing a substrate composed of an RFeB sintered body by orienting an RFeB magnet powder containing 28% to 33% by mass of a rare-earth element R, 0% to 2.5% by mass of Co (i.e., Co may not be contained), 0.3% to 0.7% by mass of Al, and 0.9% to 1.2% by mass of B, with the balance being Fe, in a magnetic field and then sintering the powder;
a first aging treatment step of heating the substrate to a first aging temperature that is a temperature falling within the range of 700° C. to 900° C.; and
a second aging treatment step of heating the substrate after being subjected to the first aging treatment step, to a second aging temperature that is a temperature falling within the range of 530° C. to 580° C.,
in which the substrate preparation step, the first aging treatment step and the second aging treatment step are performed so that the finally obtained RFeB sintered magnet has a content of O being less than 1,500 ppm. At least a part of these steps are preferably performed in a vacuum (e.g., 10 Pa or less) or inert gas atmosphere (e.g., nitrogen gas, argon gas, etc. with at most 30 ppm of oxygen gas in a partial pressure). The substrate preparation step is preferably performed in a nitrogen gas or argon gas atmosphere with at most 30 ppm of oxygen gas in a partial pressure. The first and second aging treatment steps are preferably performed in an argon gas atmosphere or in a vacuum (10 Pa or less).
The second aging temperature can be a temperature falling within the range of 530° C. to 560° C.
In the RFeB sintered magnet according to the present invention, a substrate composed of an RFeB sintered body is manufactured by using an RFeB sintered magnet powder containing 0.3% to 0.7% by mass of Al and then, the substrate was heated to a temperature falling within the range of 700° C. to 900° C. in the first aging treatment step and further heated to a temperature falling within the range of 530° C. to 580° C., preferably within the range of 560° C. to 580° C. in the second aging treatment step. Accordingly, an RFeAl phase is formed at a crystal grain boundary. Incidentally, the RFeAl phase is not formed at the crystal grain boundary at the time when the first aging treatment step is finished. Since a magnetic interaction between Fe atoms is weakened by the replacement of a part of the Fe atom by an Al atom in the RFeAl phase, saturation magnetization becomes small.
However, in the case where a large amount of oxygen is present around the RFeB magnet powder in the substrate preparation step, a large amount of a rare earth oxide is formed in the RFeB magnet powder and, at the time when the rare earth oxide is dissolved in the sintering step, a large amount of Al is incorporated into the rare earth oxide. In the case where a large amount of Al is incorporated into the rare earth oxide as such, the RFeAl phase is not formed at a crystal grain boundary. Therefore, in the present invention, the content of O as an impurity in the finally obtained RFeB sintered magnet is controlled to less than 1,500 ppm. The content of O is desirably less than 1,000 ppm.
In the RFeB sintered magnet according to the present invention, an R-rich phase other than the RFeAl phase may be present in a crystal grain boundary. The R-rich phase is a phase in which the content of the rare-earth element is higher than that in R2Fe14B that constitutes crystal grains of the RFeB sintered magnet. Examples of the R-rich phase include those in which at least one element selected from the group consisting of Fe, Co, Al, and Ga is solid-solved in a rare-earth oxide (R2O3). Fe solid-solved in the R-rich phase has ferromagnetism but, in the RFeB sintered magnet according to the present invention, since the RFeAl phase is formed in a crystal grain boundary, Fe in the crystal grain boundary is incorporated into the RFeAl phase and the concentration of Fe solid-solved in the R-rich phase can be lowered, so that saturation magnetization of the R-rich phase (i.e., saturation magnetization of Fe solid-solved therein) can be make small The R-rich phase having such a low Fe concentration is diffused over the whole crystal grain boundary by heating the substrate at 530° C. to 580° C. in the second aging treatment step. Especially, the R-rich phase can be diffused even to small spaces between two crystal grains.
As described above, in the RFeB sintered magnet according to the present invention, the RFeAl phase (and the R-rich phase) having a small saturation magnetization is present in a crystal grain boundary. Therefore, even when a reverse magnetic field is applied to the RFeB sintered magnet and the magnetization of a certain crystal grain is inverted, the action of inverting the magnetization of an adjacent crystal grain through the crystal grain boundary is weakened, so that such a high coercivity as 16 kOe or more can be achieved. Furthermore, since Al is suitably used without using any heavy rare-earth element RH and Ga as far as possible and Al is more inexpensive than them, increase in cost can be suppressed.
In the case where the value of x in R6Fe14-xAlx of the RFeAl phase is lower than 0.5, since the saturation magnetization by Fe in the RFeAl phase increases, the magnetic interaction to invert the magnetization of an adjacent crystal grain becomes strong. On the other hand, in the case where the value of x is higher than 3.5, the amount of Fe incorporated into the RFeAl phase decreases and the amount of Fe solid-solved in the R-rich phase in the crystal grain boundary accordingly increases to enlarge the saturation magnetization of the R-rich phase, so that the magnetic interaction to invert the magnetization of an adjacent crystal grain becomes strong. Therefore, in the RFeB sintered magnet according to the present invention, the value of x in R6Fe14-xAlx of the RFeAl phase is desirably controlled to the range of 0.5 to 3.5.
It is preferable that the RFeB sintered magnet according to the present invention further contains 0.1% to 0.5% by mass of Cu (copper), the total of the contents of Cu and Al exceeds 0.5% by mass, and the content of Al is larger than the content of Cu. According to this configuration, the wettability of a grain boundary phase is improved (optimized) and the grain boundary phase can be homogeneously dispersed at the second aging treatment step, so that the coercivity is more improved.
Moreover, the RFeB sintered magnet according to the present invention preferably further contains 0.05% to 0.35% by mass of Zr. According to this configuration, a squareness ratio can be made high. Here, the squareness ratio is represented by the ratio Hk90/iHc of the reverse magnetic field Hk90 when magnetization becomes 90% of residual magnetic flux density Br to the coercivity (reverse magnetic field when magnetization becomes 0) iHc in the second quadrant of magnetization curve (demagnetization curve). A higher squareness ratio means that variation of magnetization resulting from variation of a magnetic field is smaller and a magnet has more stable characteristics in a variable magnetic field.
According to the present invention, there can be obtained an RFeB sintered magnet having a high coercivity without using a heavy rare-earth element RH and Ga that are expensive additive elements as far as possible.
Referring to
(1) Composition:
The RFeB sintered magnet of the present embodiment contains, as a whole composition, 28% to 33% by mass, preferably 29% to 32% by mass of a rare-earth element R, 0% to 2.5% by mass, preferably 0% to 1.5% by mass of Co (cobalt), 0.3% to 0.7% by mass, preferably 0.4% to 0.5% of Al (aluminum), and 0.9% to 1.2% by mass of B (boron), and less than 1,500 ppm, preferably less than 1,000 ppm of O (oxygen), and contains Fe (iron) as the balance. Co may not be contained. As the rare-earth element R, a light rare-earth element such as Nd or Pr can be suitably used. Moreover, it is not necessary to use a heavy rare-earth element RH as the rare-earth element R. However, the RFeB sintered magnet of the present embodiment may contain a heavy rare-earth element RH as a part of the rare-earth element R. Furthermore, the RFeB sintered magnet of the present embodiment may further contain, in addition to these elements, 0.1% to 0.5% by mass of Cu and/or 0.05% to 0.35% by mass of Zr. In the case of containing Cu, it is preferable that the total of the contents of Cu and Al exceeds 0.5% by mass and the content of Al is larger than the content of Cu. Moreover, in addition to these elements, the RFeB sintered magnet of the present embodiment may further contain aforementioned unavoidable impurities.
The crystal grain boundary of the RFeB sintered magnet of the present embodiment contains an RFeAl phase and may further contain an R-rich phase. The RFeAl phase has a composition represented by R6Fe14-xAlx (0.5≤x≤3.5). Typical examples of the R-rich phase include a phase in which at least one element selected from the group consisting of Fe, Co, Al, and Ga is solid-solved in R2O3. Here, the concentration of Fe solid-solved in the R-rich phase becomes lower than the concentration of Fe solid-solved in the R-rich phase in the crystal grain boundary of conventional RFeB sintered magnets owing to the incorporation of Fe into the RFeAl phase.
(2) Production Method:
The RFeB sintered magnet of the present embodiment can be produced by the method to be described below. Each step to be mentioned below is performed so that the finally obtained RFeB sintered magnet has a content of O being less than 1,500 ppm, and at least a part of these steps is preferably performed under vacuum or in an inert gas atmosphere.
First, an RFeB alloy lump 11 containing an rare-earth element R, Co (which may not be contained), Al, B and Fe, and, if necessary, Cu and/or Zr in the same contents as those of the RFeB sintered magnet to be produced is prepared, for example, by a strip-cast method. Next, the RFeB alloy lump 11 is exposed to a hydrogen gas to occlude hydrogen molecules ((a) of
Next, the RFeB magnet powder 13 is accommodated in a mold 19 having a shape corresponding to the RFeB sintered magnet to be produced. A magnetic field is applied to the RFeB magnet powder 13 in the mold 19 to orient the RFeB magnet powder 13 ((d) of
Here, the hydrogen molecules contained in the grains of the RFeB magnet powder 13 are released to the outside by the heating for sintering. On the occasion, carbon present in the RFeB magnet powder 13 as an impurity reacts with the hydrogen molecules to form a gas. Carbon can be removed from the RFeB magnet powder 13 in this manner In this case, in order to reduce or prevent the elimination of the hydrogen molecules from the grains of the RFeB magnet powder 13 before the reaction with carbon, it is preferable that operations performed in a temperature range of from room temperature to a predetermined temperature (e.g., 450° C.) in the course of elevating temperature to a sintering temperature are performed in an inert gas atmosphere, and thereafter the temperature is elevated to the sintering temperature in a vacuum atmosphere. Here, the purpose of employing a vacuum atmosphere is to remove the gas generated by the reaction of the hydrogen molecules with carbon. The mold 19 used can be made of a material having thermal resistance capable of withstanding at the sintering temperature.
At the time of manufacturing the RFeB sintered body, compression molding is generally performed (press process) during or after orientation of the RFeB magnet powder in a magnetic field. In the present embodiment, however, the RFeB magnet powder 13 is sintered without performing compression molding during or after the orientation of the RFeB magnet powder (PLP (press-less process)). In the PLP, since it is not necessary to use a press machine for performing compression molding, working space can be made small. Therefore, it is easy to make the working space an inert gas atmosphere or a vacuum atmosphere. Then, even in the case where the grain size of the RFeB magnet powder 13 is made small (the surface area of the grains is made large), the oxidation of the RFeB magnet powder 13 hardly proceeds. Therefore, the oxygen content of the prepared substrate can be decreased and thus, a rare-earth oxide is hardly formed in the substrate. Accordingly, Al is hardly incorporated into the rare-earth oxide, so that the RFeAl phase can be formed at the crystal grain boundary. Moreover, when the average grain size of the RFeB magnet powder 13 becomes close to the average gran size of the crystal grains in the obtained RFeB sintered magnet by making the grain size of the RFeB magnet powder 13 small, the average grain size of the crystal grains in the RFeB sintered magnet also decreases as the average grain size of the RFeB magnet powder 13 decreases, whereby the coercivity of the RFeB sintered magnet can be improved. Incidentally, the RFeB sintered magnet according to the present invention can be also manufactured by using a press process but, as mentioned so far, it is desirable to use the PLP for decreasing the oxygen content of the substrate.
After the substrate 14 is prepared as mentioned above, the substrate 14 is once cooled to room temperature and then heated to a first aging temperature that is a temperature falling within the range of 700° C. to 900° C. ((g) of
Next, the substrate 14 subjected to the first aging treatment step is heated to a second aging temperature that is a temperature falling within the range of 530° C. to 580° C., preferably 560° C. to 580° C. ((h) of
In this manner, the RFeB sintered magnet 15 of the present embodiment can be obtained ((i) of
(3) Examples of RFeB Sintered Magnet of Present Embodiment
Examples of producing the RFeB sintered magnet of the present embodiment will be described below.
Seven kinds of RFeB alloy lumps each having the respective composition (measurement values) described in Table 1 were each manufactured by a strip casting method (hereinafter referred to as alloys 1 to 7). Here, “IRE” in Table 1 means the sum of the contents of all rare-earth elements (Total Rare-Earth) and here, is the sum of the contents of Nd (neodymium), Pr (praseodymium), Dy (dysprosium), and Tb (terbium). Incidentally, rare-earth elements other than these four kinds are not contained in the alloys 1 to 7 except for those contained as unavoidable impurities. The alloys 1 to 7 may contain unavoidable impurities in addition to the elements mentioned in Table 1.
Each of the alloys 1 to 7 was subjected to a rough pulverization and a fine pulverization under the aforementioned conditions, to thereby prepare the respective RFeB magnet powder 13. The RFeB magnet powder 13 was filled into a mold 19 so that filling density be 3.4 g/cm3 and then, the RFeB magnet powder 13 was oriented in a magnetic field. Subsequently, the RFeB magnet powder 13 was heated from room temperature to a sintering temperature between 985° C. and 995° C. while being still filled in the mold 19, maintained at the temperature for 4 hours and then, cooled to room temperature, thereby preparing a substrate 14. The sintering was performed in an argon gas atmosphere from room temperature to 450° C. and thereafter performed in a vacuum atmosphere (10 Pa or less). The respective substrate 14 obtained from the alloys 1 to 7 was heated at a first aging temperature of 800° C. for 30 minutes, lowered in temperature to a second aging temperature that was 540° C. or 560° C. (described in Table 1 for each alloy) and then maintained for 90 minutes at that temperature, followed by rapidly cooling, to thereby produce an RFeB sintered magnet 15. The RFeB sintered magnets manufactured from the alloys 1 to 7 were called samples of Examples 1 to 7, respectively.
In addition, as Comparative Example 1, an RFeB sintered magnet was manufactured in the same manner as in Example 1 by using the alloy 1 except that the content of O was made larger than that of Examples 1 to 7 and Comparative Example 2. In addition, as Comparative Examples 2 and 3, RFeB sintered magnets were manufactured in the same manner as in Example 1 except for using an alloy A having the composition described in Table 1. The RFeB sintered magnet of Comparative Example 3 was manufactured so as to have a higher content of O than that of Examples 1 to 7 and Comparative Example 2. Here, the content of O in the obtained RFeB sintered magnet can be adjusted by controlling the production environment in the steps from the pulverization of the RFeB ally lump 11 to the filling of the RFeB magnetic powder 13 into the mold 19. The second aging temperature was 540° C. (Comparative Example 1) or 520° C. (Comparative Examples 2 and 3). The alloy A has a content of Al of 0.16% by mass, which falls outside the range of the composition of the RFeB sintered magnet of the present invention.
Table 2 shows the results of measuring the composition of the manufactured samples of Examples 1 to 7 and Comparative Examples 1 to 3. Moreover, Table 3 shows coercivity iHc, squareness ratio SQ, and values of Hk90 measured for determining the squareness ratio SQ of each of these samples. Here, Hk90 is a value of reverse magnetic field at the time when magnetization becomes 90% of residual magnetic flux density Br, in the second quadrant of the magnetization curve (demagnetization curve). The squareness ratio SQ is determined by Hk90/iHc.
In all of the samples of Examples 1 to 7, the composition of elements mentioned in Table 2 satisfies the compositional requirement in the RFeB sintered magnet of the present invention. In contrast, in the samples of Comparative Examples 1 and 3, the content of 0 does not satisfy the requirement of the present invention (i.e., less than 1,500 ppm). Moreover, in the samples of Comparative Examples 2 and 3, the content of Al does not satisfy the requirement of the present invention (i.e., 0.3% to 0.7% by mass). On the other hand, in the samples of Comparative Examples 2 and 3, the contents of the elements other than Al and O are very close to the respective contents of the elements in the sample of Example 2.
Among these Examples, when the samples of Examples 1 to 6 where Dy is not contained are compared with the samples of Comparative Examples in the coercivity iHc, all of the samples of Examples 1 to 6 showed the coercivity of from 16.8 kOe to 18.2 kOe that are larger than 16.0 kOe, but all of the samples of Comparative Examples 1 to 3 showed the coercivity of from 14.5 kOe to 15.7 kOe that are smaller than 16.0 kOe. Particularly, the sample of Example 2 where the contents of the elements other than Al and O are very close to those in Comparative Examples 2 and 3 as mentioned above showed such a high coercivity iHc as 18.2 kOe, which is remarkably higher than that in Comparative Examples 2 and 3.
Moreover, the samples of Examples 3 to 5 contains 0.08% to 0.11% by mass of Zr and showed the values of the squareness ratio SQ being higher (94.6% to 95.4%) than those in the other samples (Examples 1 and 2 and Comparative Examples 1 to 3). The sample of Example 7 contains 2.50% by mass of Dy and showed the value of the coercivity iHc being higher than the values in the other samples.
Next, an X-ray diffraction measurement was performed for the samples of Examples 1 and 2 and Comparative Example 2, and the results thereof are shown in
Next, the sample of Example 2 was subjected to an analysis using a wavelength dispersive X-ray spectroscopy (WDX), and in six measurement points arbitrarily selected in crystal grain boundaries and containing all of three elements of R, Fe and Al, compositional ratios of these three kinds of elements, Co and Cu were determined. Table 4 shows the results.
In these six measurement points, the ratio of the content of the R atom to the sum of the contents of four atoms of Fe, Co, Al, and Cu is close to 6:14 and thus, it is considered that an RFeAl phase was formed in crystal grain boundaries.
In the case where an RFeAl phase is formed in a crystal grain boundary, the amount of Fe solid-solved in the R-rich phase is decreased. Since magnetic interaction among crystal grains is decreased due to the small saturation magnetization of the RFeAl phase and due to the small amount of Fe solid-solved in the R-rich phase, the coercivity of the RFeB sintered magnet of the present embodiment becomes high.
Next, by using the substrate 14 prepared from the RFeB magnet powder obtained from the alloy 3, samples were prepared under a plurality of conditions varying in the temperature and heating time in the first aging treatment step and the second aging treatment step, and coercivity was measured for each samples. The following describes the results.
The graph of (a) of
The graph of (b) of
The graph of (c) of
The graph of (d) of
As described above, from the experimental results shown in
Next, the substrate 14 prepared by using the RFeB magnet powder obtained from the alloy 3 was subjected to an aging treatment where the first aging temperature was 800° C., the heating time at the first aging treatment step was 30 minutes, the second aging temperature was 540° C., and the heating time in the second aging treatment step (the time for which temperature was maintained at 540° C.) was 30 minutes. Thereafter, samples of the RFeB sintered magnet were manufactured for a plurality of examples varying in a cooling rate at the time of cooling the substrate 14 from the second aging temperature to 100° C. In addition, as Comparative Examples, for the case where the substrate 14 prepared by using the RFeB magnet powder obtained from the alloy 3 was subjected to the second aging treatment step without being subjected to the first aging treatment step, a plurality of samples of the RFeB sintered magnet were manufactured similarly varying in the cooling rate.
The present invention have been described above based on embodiments and Examples but specific configurations should not be construed as being limited to these embodiments and Examples. The scope of the present invention is shown by not only the description of the embodiments and Examples mentioned above but also Claims, and all changes within meanings and scopes equivalent to Claims are included therein.
The present application is based on Japanese Patent Application No. 2018-208615 filed on Nov. 6, 2018 and Japanese Patent Application No. 2019-154463 filed on Aug. 27, 2019, and the contents thereof are incorporated herein by reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| JP2018-208615 | Nov 2018 | JP | national |
| JP2019-154463 | Aug 2019 | JP | national |
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| Number | Date | Country | |
|---|---|---|---|
| 20200143965 A1 | May 2020 | US |
