Patent Application
20160042848
The present invention relates to an R-T-B-based sintered magnet.
An R-T-B-based sintered magnet including an Nd2Fe14B type compound as a main phase (R is at least one of rare-earth elements and inevitably includes Nd, and T is a transition metal element and inevitably includes Fe) has been known as a permanent magnet with the highest performance among permanent magnets, and has been used in various motors for hybrid vehicles, electric vehicles, and home appliances.
However, in the R-T-B-based sintered magnet, coercivity HcJ (hereinafter sometimes simply referred to as “HcJ”) decreases at an elevated temperature to cause irreversible thermal demagnetization. Therefore, when used particularly in motors for hybrid vehicles and electric vehicles, there is a need to maintain high HcJ even at an elevated temperature.
To increase HcJ, numerous heavy rare-earth elements (mainly, Dy) have hitherto been added to the R-T-B-based sintered magnet. However, there arose a problem that a residual magnetic flux density Br (hereinafter sometimes simply referred to as “Br”) decreases. Therefore, there has recently been employed a method in which heavy rare-earth elements are diffused from the surface into the inside of the R-T-B-based sintered magnet to thereby increase the concentration of the heavy rare-earth elements at the outer shell part of main phase crystal grains, thus obtaining high HcJ while suppressing a decrease in Br.
Dy has problems such as unstable supply and price fluctuations because of restriction of the producing district. Therefore, there is a need to develop technology for improving HcJ of the R-T-B-based sintered magnet without using heavy rare-earth elements such as Dy.
Patent Document 1 discloses that a B concentration is decreased as compared with a conventional R-T-B-based alloy and one or more metal elements M selected from among Al, Ga, and Cu are included to form a R2T17 phase, and a volume fraction of a transition metal-rich phase (R6T13M) formed from the R2T17 phase as a raw material is sufficiently secured to obtain an R-T-B-based rare-earth sintered magnet having high coercivity while suppressing the content of Dy.
Patent Document 1: WO 2013/008756 A
However, Patent Document 1 had a problem that since the B concentration is significantly decreased than usual, an existence ratio of a main phase decreases, leading to a significant reduction in Br. Although HcJ increases, HcJ is insufficient to satisfy requirements in recent days.
The present invention has been made so as to solve the above problems and an object thereof is to provide an R-T-B-based sintered magnet having high Br and high HcJ without using Dy.
An aspect 1 of the present invention is directed to an R-T-B based sintered magnet which includes an Nd2Fe14B type compound as a main phase, and comprises the main phase, a first grain boundary phase located between two main phases, and a second grain boundary phase located between three or more main phases, the R-T-B based sintered magnet comprising:
R: 29.0% by mass or more and 31.5% by mass or less (R being Nd and/or Pr),
B: 0.86% by mass or more and 0.90% by mass or less,
Ga: 0.4% by mass or more and 0.6% by mass or less,
Al: 0.5% by mass or less (including 0% by mass), and
balance being T (T is a transition metal element and inevitably includes Fe) and inevitable impurities.
An aspect 2 of the present invention is directed to the R-T-B based sintered magnet in the aspect 1, which further includes:
Cu: 0.05% by mass or more and 0.20% by mass or less.
An aspect 3 of the present invention is directed to the R-T-B based sintered magnet in the aspect 1 or 2, wherein the content of B is 0.87% by mass or more and 0.89% by mass or less.
An aspect 4 of the present invention is directed to the R-T-B based sintered magnet in any one of the aspects 1 to 3, wherein an R—Ga phase including R: 70% by mass or more and 95% by mass or less, Ga: 5% by mass or more and 30% by mass or less, and Fe: 20% by mass or less (including 0) is present in the first grain boundary phase.
An aspect 5 of the present invention is directed to the R-T-B based sintered magnet in the aspect 2 or the aspect 3 citing the aspect 2, wherein an R—Ga phase including R: 70% by mass or more and 95% by mass or less, Ga: 5% by mass or more and 30% by mass or less, and Fe: 20% by mass or less (including 0), and an R—Ga—Cu phase in which Ga of the R—Ga phase is partially replaced with Cu are present in the first grain boundary phase.
An aspect 6 of the present invention is directed to the R-T-B based sintered magnet in any one of the aspects 1 to 5, which includes a first grain boundary phase free from an R-T-Ga phase composed of R6Fe13Ga1.
According to the present invention, it is possible to provide an R-T-B based sintered magnet having high Br and high HcJ without using Dy.
The inventors have intensively been studied so as to solve the above problems and found that, as shown in the aspect 1 or 2 of the present invention, an R-T-B based sintered magnet having high Br and high HcJ is obtained without using Dy by optimizing the contents of R, B, and Ga. As a result of an analysis of the R-T-B based sintered magnet thus obtained, the inventors have found that an R—Ga phase is present in a first grain boundary phase located between two main phases (hereinafter sometimes referred to as a “two-grain boundary phase”) when including no Cu, and an R—Ga phase and an R—Ga—Cu phase are present in a first grain boundary phase located between two main phases when including Cu. As a result of a more detailed analysis, they have found that a first grain boundary phase free from an R-T-Ga phase is included.
There are still unclear points regarding the mechanism in which high Br and high HcJ are obtained without using Dy by the existence of an R—Ga phase or an R—Ga and an R—Ga—Cu phase in a first grain boundary phase, and inclusion of a first grain boundary phase free from an R-T-Ga phase. A description will be made on the mechanism proposed by the inventors based on the findings they have had so far. It is to be noted that the description regarding the following mechanism is not intended to limit the technical scope of the present invention.
The R-T-B based sintered magnet enables an increase in Br by increasing an existence ratio of an Nd2Fe14B type compound which is a main phase. To increase the existence ratio of the Nd2Fe14B type compound, the amount of R, the amount of T, and the amount of B may be made closer to a stoichiometric ratio of the Nd2Fe14B type compound. If the amount of B for formation of the Nd2Fe14B type compound is lower than the stoichiometric ratio, a soft magnetic R2T17 phase is precipitated in a grain boundary phase, leading to a rapid reduction in HcJ. However, if Ga is included in the magnet composition, an R-T-Ga phase is formed in place of an R2T17 phase, thus enabling suppression of a reduction in HcJ.
The reason why a reduction in HcJ is suppressed by formation of an R-T-Ga phase was initially supposed that an R2T17 phase causing a rapid reduction in HcJ disappears and also the R-T-Ga phase thus formed has no or extremely weak magnetization. However, it becomes apparent that the R-T-Ga phase also has slight magnetization and, if the R-T-Ga phase excessively is present in the grain boundary phase, particularly, two-grain boundary phase in charge of HcJ, magnetization prevents HcJ from increasing. It also becomes apparent that an R—Ga phase is formed when including no Cu along with the formation of the R-T-Ga phase, while the R—Ga phase and the R—Ga—Cu phase are formed when including Cu along with the formation of the R-T-Ga phase.
Thus, it was supposed that HcJ can be further increased if the R—Ga phase or the R—Ga and the R—Ga—Cu phase can be formed while suppressing formation of the R-T-Ga phase in the two-grain boundary phase. It was also supposed that a reduction in Br can also be suppressed since the amount of B does not cause a significant decrease in existence ratio of a main phase as a result of suppression of formation of the R2T17 phase so as to suppress formation of the R-T-Ga phase. However, if formation of the R-T-Ga phase is excessively suppressed, it is impossible to form the R—Ga phase or the R—Ga and the R—Ga—Cu phase. Thus, by controlling the amount of R and the amount of B within an appropriate range to adjust the precipitation amount of an R2T17 phase, and also by controlling the amount of Ga within an optimum range corresponding to the precipitation amount of the R2T17 phase, the R—Ga phase or the R—Ga and the R—Ga—Cu phase can be formed while suppressing the R-T-Ga phase from forming as small as possible. Whereby, it becomes possible to obtain a structure in which an R—Ga phase or an R—Ga and an R—Ga—Cu phase is (are) present in the two-grain boundary phase in the entire R-T-B based sintered magnet, and also numerous two-grain grain boundaries free from an R-T-Ga phase are present. Whereby, suppression of an increase in HcJ due to the R-T-Ga phase is reduced and also a decrease in existence ratio of a main phase is suppressed, thus making it possible to more certainly obtain an R-T-B based sintered magnet having high Br and high HcJ.
The R-T-B based sintered magnet according to one embodiment of the present invention comprises:
R: 29.0% by mass or more and 31.5% by mass or less (R being Nd and/or Pr),
B: 0.86% by mass or more and 0.90% by mass or less,
Ga: 0.4% by mass or more and 0.6% by mass or less,
Al: 0.5% by mass or less (including 0% by mass), and
balance being T (T is a transition metal element, and inevitably includes Fe) and inevitable impurities.
Alternatively, the R-T-B based sintered magnet according to one embodiment of the present invention comprises:
R: 29.0% by mass or more and 31.5% by mass or less (R being Nd and/or Pr),
B: 0.86% by mass or more and 0.90% by mass or less,
Ga: 0.4% by mass or more and 0.6% by mass or less,
Cu: 0.05% by mass or more and 0.20% by mass or less,
Al: 0.5% by mass or less (including 0% by mass), and
balance being T (T is a transition metal element, and inevitably includes Fe) and inevitable impurities.
The present invention can exert the effect capable of obtaining high Br and high HcJ by combining the amount of R, the amount of B, and the amount of Ga within the above range. If any one of the amount of R, the amount of B, and the amount of Ga deviates from the above range, formation of the R-T-Ga phase is excessively suppressed. Accordingly, in the entire R-T-B based sintered magnet, the R—Ga phase, or the R—Ga and the R—Ga—Cu phase is/are not formed in a two-grain boundary phase, whereas a two-grain boundary phase free from an R-T-Ga phase decreases (two-grain boundary phase including an R-T-Ga phase becomes dominant), thus failing to obtain high Br and high HcJ.
R is Nd and/or Pr. The content of R is set within a range of 29.0% by mass or more and 31.5% by mass or less. The content of B is set within a range of 0.86% by mass or more and 0.90% by mass or less. The content of B is preferably 0.87% by mass or more and 0.89% by mass or less. The content of Ga is set within a range of 0.4% by mass or more and 0.6% by mass or less. Balance T is a transition metal element, and inevitably includes Fe. Examples of the transition metal element except for Fe include Co. It is not preferable that the amount of Co substitution of more than 10% leads to a reduction in Br. Examples of the transition metal element may further include a small amount of V, Cr, Mn, Zr, Nb, Mo, Hf, Ta, W, and the like.
In addition to each element mentioned above, 0.05% by mass or more and 0.20% by mass or less of Cu may be included. Inclusion of Cu lead to formation of an R—Ga—Cu phase in the two-grain boundary phase, together with an R—Ga phase. Formation of the R—Ga—Cu phase leads to a further increase in HcJ as compared with the case of the R—Ga phase alone. The content of Cu is preferably 0.08% by mass or more and 0.15% by mass or less. The magnet may have the same degree of Al content as usual. The range where known effects are exerted is set at 0.5% by mass or less (including 0% by mass), and preferably 0.3% by mass or less.
In the present invention, the R-T-Ga phase may include: R: 15% by mass or more and 65% by mass or less (preferably, R: 40% by mass or more and 65% by mass or less), T: 20% by mass or more and 80% by mass or less, Ga: 2% by mass or more and 20% by mass or less (when the content of R is 40% by mass or more and 65% by mass or less, the content of T may be 20% by mass or more and 55% by mass or less, and the content of Ga may be 2% by mass or more and 15% by mass or less), and examples thereof include an R6Fe13Ga1 compound. More specifically, the R-T-Ga phase may be entirely composed of an R6Fe13Ga1 compound or may include an R6Fe13Ga1 compound, as long as it includes R: 15% by mass or more and 65% by mass or less (preferably, R: 40% by mass or more and 65% by mass or less), T: 20% by mass or more and 80% by mass or less, Ga: 2% by mass or more and 20% by mass or less (when the content of R is 40% by mass or more and 65% by mass or less, the content of T may be 20% by mass or more and 55% by mass or less, and the content of Ga may be 2% by mass or more and 15% by mass or less). The R-T-Ga phase may include other elements except for the above-mentioned R, T, and Ga. The R-T-Ga phase may contain, as these other elements, one or more elements selected from such as Al and Cu. The R—Ga phase may include 70% by mass or more and 95% by mass or less of R, 5% by mass or more and 30% by mass or less of Ga, and 20% by mass or less (including 0) of Fe, and examples thereof include an R3Ga1 compound. More specifically, the R—Ga phase may be entirely composed of an R3Ga1 compound or may include an R3Ga1 compound, as long as it includes R: 70% by mass or more and 95% by mass or less, Ga: 5% by mass or more and 30% by mass or less, and Fe: 20% by mass or less (including 0). The R—Ga—Cu phase may be a phase in which Ga of the R—Ga phase is partially replaced with Cu, and examples thereof include an R3(Ga,Cu)1 compound. More specifically, the R—Ga—Cu phase may be entirely composed of an R3(Ga,Cu)1 compound or may include an R3(Ga,Cu)1 compound, as long as Ga of the R—Ga phase is partially replaced with Cu.
An example of a method for producing an R-T-B based sintered magnet will be described. The method for producing an R-T-B based sintered magnet includes a step of obtaining an alloy powder, a molding step, a sintering step, and a heat treating step. Each step will be described below.
(1) Step of obtaining Alloy Powder
Metals or alloys of the respective elements are prepared so as to obtain the above-mentioned composition, and a flaky alloy is produced from them using a strip casting method. The flaky alloy thus obtained is subjected to hydrogen decrepitation to obtain a coarsely crushed powder having a size of 1.0 mm or less. Next, the coarsely crushed powder is finely pulverized by a jet mill to obtain a finely pulverized powder (alloy powder) having a particle diameter D50 (value obtained by a laser diffraction method using an air flow dispersion method (median size)) of 3 to 7 μm. A known lubricant may be used as a pulverization assistant in a coarsely crushed powder before jet mill pulverization, or an alloy powder during and after jet mill pulverization.
Using the alloy powder thus obtained, molding in a magnetic field is performed to obtain a molded body. The molding in a magnetic field may be performed using known optional methods of molding in a magnetic field including a dry molding method in which a dry alloy powder is loaded in a cavity of a die and then molded while applying a magnetic field, and a wet molding method in which a slurry containing the alloy powder dispersed therein is injected in a cavity of a die and then molded while discharging a dispersion medium of the slurry.
The molded body is sintered to obtain a sintered magnet. A known method can be used to sinter the molded body. To avoid oxidation due to an atmosphere during sintering, sintering is preferably performed in a vacuum atmosphere or an atmospheric gas. It is preferable to use, as the atmospheric gas, an inert gas such as helium or argon.
The sintered magnet thus obtained is preferably subjected to a heat treating for the purpose of improving magnetic properties. Known conditions can be employed for heat treating temperature, heat treating time, and the like. To adjust the size of the sintered magnet, the magnet obtained may be subjected to machining such as grinding. In that case, the heat treating may be performed before or after machining. The sintered magnet may also be subjected to a surface treatment. The surface treatment may be a known surface treatment, and it is possible to perform surface treatments, for example, Al vapor deposition, Ni electroplating, resin coating, and the like.
The present invention will be described in more detail below by way of Examples, but the present invention is not limited thereto.
Nd having a purity of 99.5% by mass or more, electrolytic iron, electrolytic Co, Al, Cu, Ga, and ferroboron alloy were prepared so that the composition of a sintered magnet became each composition shown in Table 1, and then these raw materials were melted and subjected to casting by a strip casting method to obtain a flaky alloy having a thickness of 0.2 to 0.4 mm. The flaky alloy thus obtained was subjected to hydrogen embrittlement in a pressurized hydrogen atmosphere and then subjected to a dehydrogenation treatment of heating to 550° C. in vacuum and cooling to obtain a coarsely crushed powder. To the coarsely crushed powder thus obtained, zinc stearate was added as a lubricant in the proportion of 0.04% by mass based on 100% by mass of the coarsely crushed powder, followed by mixing. Using an air flow-type pulverizer (jet milling machine), the mixture was subjected to dry pulverization in a nitrogen gas flow to obtain a finely pulverized powder (alloy powder) having a particle diameter D50 (median size) of 4 μm. The oxygen concentration in a nitrogen gas during pulverization was controlled to 50 ppm or less. The particle diameter D50 is the value obtained by a laser diffraction method using an air flow dispersion method.
The alloy powder thus obtained was mixed with a dispersion medium to prepare a slurry. Normal dodecane was used as a solvent, and methyl caprylate was added as a lubricant. Regarding the concentration of the slurry, the proportion of the alloy powder was set at 70% by mass and that of the dispersion medium was set at 30% by mass, while the proportion of the lubricant was set at 0.16% by mass based on 100% by mass of the alloy powder. The slurry was molded in a magnetic field to obtain a molded body. The magnetic field during molding was static magnetic field set at 0.8 MA/m, and the molding pressure was set at 5 MPa. A molding device used was a so-called perpendicular magnetic field molding device (transverse magnetic field molding device) in which a magnetic field application direction and a pressuring direction are perpendicular to each other.
The molded body thus obtained was sintered in vacuum at 1,020° C. for 4 hours to obtain a sintered magnet. The sintered magnet had a density of 7.5 Mg/m3 or more. The sintered body thus obtained was subjected to a heat treating of retaining at 800° C. for 2 hours and cooling to room temperature, followed by retaining at 500° C. for 2 hours and cooling to room temperature. The sintered magnet after the heat treating was machined to produce samples of 7 mm in length×7 mm in width×7 mm in thickness, and Br and HcJ of each sample were measured by a B-H tracer. The measurements results are shown in Table 1.
As is apparent from Table 1, an R-T-B based sintered magnet having high Br and high HcJ is obtained by adjusting the composition within the following range where Nd: 29.0% by mass or more and 31.5% by mass or less, B: 0.86% by mass or more and 0.90% by mass or less, and Ga: 0.4% by mass or more and 0.6% by mass or less. It is apparent that HcJ is more increased than the case of including no Cu (sample No. 19) by including 0.05% by mass or more and 0.20% by mass or less of Cu (samples Nos. 20 to 22). Since most excellent Br and HcJ are obtained when the amount of B is about 0.88% by mass, it is considered that the amount of B is preferably 0.87% by mass or more and 0.89% by mass or less.
For sample No. 14 (Example of the present invention) and sample No. 2 (Comparative Example) in Table 1, structure observation by FE-TEM (field-emission transmission electron microscope) was performed. The results are shown in
In
The results shown in Table 2 reveal that, in sample No. 14 which is Example of the present invention, an R-T-Ga phase (Nd6Fe13Ga1 compound) is present at point A (grain boundary multi-point), an R—Ga phase (Nd3Ga1 compound) is present at point B (two-grain boundary phase), and point C indicates a main phase. Thus, it is apparent that an R—Ga phase is present in a first grain boundary phase in an R-T-B based sintered magnet according to the present invention. In consideration of the fact that the content of Fe at point B is 20% or less, it is apparent that an R-T-Ga phase is not present at point B, namely, a first grain boundary phase free from an R-T-Ga phase is included.
The results shown in Table 2 reveal that, in sample No. 2 which is Comparative Example, an R—Ga phase (Nd3Ga1 compound) is present at point D (grain boundary multi-point), an R-T-Ga phase (Nd6Fe13Ga1 compound) is present at point E (two-grain boundary phase), and point C indicates a main phase. Thus, it is apparent that an R—Ga phase is not present in a first grain boundary phase and an R-T-Ga phase is present, in an R-T-B based sintered magnet according to Comparative Example. Sample No. 14 exhibits Br of 1.35 T and HcJ of 1,650 kA/m, and sample No. 2 exhibits Br of 1.36 T and HcJ of 890 kA/m. Thus, according to the present invention, high Br is obtained since the amount of B is set to be such an extent that does not cause a significant decrease in existence ratio of a main phase, and also high Hcj is obtained because of including a first grain boundary phase free from R-T-Ga phase obstructing an increase in HcJ existing thereon.
The R-T-B-based sintered magnet according to the present invention can be suitably employed in motors for hybrid vehicles and electric vehicles.
The present application claims priority on Japanese Patent Application No. 2013-071834 filed on Mar. 29, 2013 as a basic application, the disclosure of which is incorporated by reference herein.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2013-071834 | Mar 2013 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2014/058741 | 3/27/2014 | WO | 00 |
