JP6125687B2 - Motors, generators, and automobiles - Google Patents

Description

  Embodiments described herein relate generally to a motor, a generator, and an automobile.

As high performance permanent magnets, rare earth magnets such as Sm-Co magnets and Nd-Fe-B magnets are known. When a permanent magnet is used for a motor of a hybrid vehicle (HEV) or an electric vehicle (EV), the permanent magnet is required to have heat resistance. In HEV and EV motors, permanent magnets are used in which a part of Nd of the Nd—Fe—B magnet is replaced with Dy to improve heat resistance. Since Dy is one of rare elements, there is a demand for a permanent magnet that does not use Dy. Sm—Co magnets are known to exhibit excellent heat resistance in a system that does not use Dy, but have a disadvantage that (BH) _max is smaller than Nd—Fe—B magnets. .

Factors that determine the value of (BH) _max of the permanent magnet include the squareness of the hysteresis loop in addition to the residual magnetization and the coercive force. Even if the magnet has a large residual magnetization, if the squareness is poor, the (BH) _max value becomes lower than the theoretical value expected from the magnitude of the residual magnetization. In order to realize a high (BH) _max value, it is required that the squareness is good in addition to the large magnetization. In order to increase the magnetization of the Sm—Co magnet, it is effective to replace part of Co with Fe and increase the Fe concentration. However, in the composition region where the Fe concentration is high, the squareness of the Sm—Co magnet tends to deteriorate. Thus, there is a need for a technique for improving squareness while maintaining high magnetization and coercive force in Sm—Co magnets with high Fe concentration.

JP 2010-121167 A JP 2011-114236 A

  Problems to be solved by the present invention include a motor and a generator having permanent magnets that can improve squareness while maintaining high magnetization and coercive force of Sm—Co based magnets containing Fe, and the above The object is to provide a motor vehicle equipped with a motor or the above-mentioned generator.

The motor or generator provided in the automobile of the embodiment is
_{Formula: R (Fe p M q Cu} r Co 1-pqr) z
(In the formula, R is at least one element selected from Sm, Ce, Nd, Pr and Y, M is selected from Ti, Zr and Hf, and at least one element of which 50 atomic% or more is Zr. P, q, r and z are atomic ratios of 0.3 <p ≦ 0.45, 0.01 ≦ q ≦ 0.05, 0.01 ≦ r ≦ 0.1, 5.6 ≦ z, respectively. ≦ 9)
The permanent magnet which has the composition represented by this is comprised. The permanent magnet has a metal structure including a Th ₂ Zn ₁₇ type crystal phase, a grain boundary phase, and a platelet phase, and has a squareness ratio of 87% or more. The ratio (β / α) of the concentration of the element M (β) in the platelet phase to the concentration (α) of the element M in the grain boundary phase is in the range of more than 1 and less than 3.

It is a TEM image which expands and shows the metal structure of the permanent magnet by an embodiment. It is a figure which shows an example of the magnetization curve of the permanent magnet by embodiment. It is a figure which shows the permanent magnet motor of embodiment. It is a figure which shows the variable magnetic flux motor of embodiment. It is a figure which shows the generator of embodiment.

Hereinafter, the permanent magnet provided in the motor or the generator of the embodiment will be described. The permanent magnet of the embodiment is
_{Formula: R (Fe p M q Cu} r Co 1-pqr) z ... (1)
(In the formula, R represents at least one element selected from rare earth elements, M represents at least one element selected from Ti, Zr, and Hf, and p, q, r, and z are each in an atomic ratio of 0.8. 3 <p ≦ 0.45, 0.01 ≦ q ≦ 0.05, 0.01 ≦ r ≦ 0.1, 5.6 ≦ z ≦ 9)
It has the composition represented by these. The permanent magnet of the embodiment includes a metal structure including a Th ₂ Zn ₁₇ type crystal phase, a grain boundary phase, and a platelet phase, and the spatial distribution of Cu concentration in the grain boundary phase is set to 5 or less by standard deviation. .

  In the composition formula (1), as the element R, at least one element selected from rare earth elements including yttrium (Y) is used. Any of the elements R provides a large magnetic anisotropy to the magnet material and imparts a high coercive force. As the element R, it is more preferable to use at least one selected from samarium (Sm), cerium (Ce), neodymium (Nd), and praseodymium (Pr), and it is particularly preferable to use Sm. By setting Sm to 50 atomic% or more of the element R, the performance of the permanent magnet, particularly the coercive force, can be improved with good reproducibility. Furthermore, it is desirable that 70 atomic% or more of the element R is Sm.

  In the element R, the atomic ratio of the element R to the other elements (Fe, M, Cu, Co) is in the range of 1: 5.6 to 1: 9 (z value in the range of 5.6 to 9 / element R) In the range of 10 to 15 atomic%). When the content of the element R is less than 10 atomic%, a large amount of α-Fe phase is precipitated and a sufficient coercive force cannot be obtained. On the other hand, when the content of the element R exceeds 15 atomic%, the saturation magnetization is significantly reduced. The content of the element R is more preferably in the range of 10.2 to 14 atomic%, and further preferably in the range of 10.5 to 12.5 atomic%.

  As the element M, at least one element selected from titanium (Ti), zirconium (Zr), and hafnium (Hf) is used. By blending the element M, a large coercive force can be expressed with a composition having a high Fe concentration. The content of the element M is in the range of 1 to 5 atomic% (0.01 ≦ q ≦ 0.05) of the total amount of elements (Fe, Co, Cu, M) other than the element R. When the q value exceeds 0.05, the magnetization is remarkably reduced, and when the q value is less than 0.01, the effect of increasing the Fe concentration is small. The content of the element M is more preferably 0.012 ≦ q ≦ 0.04, and further preferably 0.015 ≦ q ≦ 0.03.

  The element M may be any of Ti, Zr, and Hf, but preferably contains at least Zr. In particular, the effect of increasing the coercive force of the permanent magnet can be further improved by using 50 atomic% or more of the element M as Zr. On the other hand, since Hf is particularly expensive among the elements M, it is preferable to reduce the amount used even when Hf is used. The Hf content is preferably less than 20 atomic% of the element M.

  Copper (Cu) is an element for causing a permanent magnet to exhibit a high coercive force. The compounding amount of Cu is in the range of 1 to 10 atomic% (0.01 ≦ r ≦ 0.1) of the total amount of elements (Fe, Co, Cu, M) other than the element R. When the r value exceeds 0.1, the magnetization is remarkably reduced, and when the r value is less than 0.01, it is difficult to obtain a high coercive force. The amount of Cu is more preferably 0.02 ≦ r ≦ 0.1, and further preferably 0.03 ≦ r ≦ 0.08.

  Iron (Fe) is mainly responsible for the magnetization of the permanent magnet. By blending a large amount of Fe, the saturation magnetization of the permanent magnet can be increased. However, if the Fe content becomes excessive, the coercive force decreases due to precipitation of the α-Fe phase. The blending amount of Fe is in the range of more than 30 atomic% and 45 atomic% or less (0.3 <p ≦ 0.45) of the total amount of elements other than element R (Fe, Co, Cu, M). The Fe content is more preferably 0.31 ≦ p ≦ 0.44, and further preferably 0.32 ≦ p ≦ 0.43.

  Cobalt (Co) is an element necessary for the magnetization of the permanent magnet and the high coercive force. Further, when a large amount of Co is contained, the Curie temperature is increased and the thermal stability of the permanent magnet is improved. If the amount of Co is small, these effects are reduced. However, if Co is excessively contained in the permanent magnet, the Fe content is relatively reduced, which may cause a decrease in magnetization. The Co content is in the range defined by p, q, and r (1-pqr).

  A part of Co is nickel (Ni), vanadium (V), chromium (Cr), manganese (Mn), aluminum (Al), silicon (Si), gallium (Ga), niobium (Nb), tantalum (Ta), And at least one element A selected from tungsten (W) may be substituted. These substitution elements contribute to improvement of magnet characteristics, for example, coercive force. However, since excessive substitution of Co with the element A may cause a decrease in magnetization, the substitution amount with the element A is set to a range of 20 atomic% or less (0 ≦ s ≦ 0.2) of Co. In addition, the magnet material of the embodiment is allowed to contain inevitable impurities such as oxides.

The SmCo-based magnet of this embodiment is a phase separation formed by using a TbCu ₇ type crystal phase (crystal phase having a TbCu ₇ type structure / 1-7 phase) as a precursor and subjecting it to an aging treatment or the like. Structure, that is, Th ₂ Zn ₁₇ type crystal phase (phase having Th ₂ Zn ₁₇ type structure / 2-17 phase) and CaCu ₅ type crystal phase (crystal phase having CaCu ₅ type structure / 1-5 phase as main phases) ) And the like, and a metallographic structure including a platelet phase. The metal structure after phase separation has a secondary structure called a cell structure.

  The metal structure described above is observed by a TEM image (transmission electron microscope image) viewed from a direction perpendicular to the easy axis direction of magnetization (c-axis direction of the crystal) of the sample after aging treatment. FIG. 1 is an example of a TEM image of the SmCo type magnet of the embodiment. As shown in FIG. 1, the structures mainly observed in the TEM image after aging treatment are the 1-7 phase (cell phase) as the main phase and the 1-5 phase (cell wall phase) as the grain boundary phase. Platelet phase. The cell phase is a crystal grain having a particle size of about 50 to 200 nm. The cell phase occupies most of the phases (all constituent phases) constituting the metal structure, and is the main phase of the SmCo type magnet. Here, the main phase means a phase having the largest volume ratio among all the constituent phases, and the volume ratio is preferably 50% or more, and more preferably 70% or more.

  The cell wall phase is a phase present in a plate shape at the grain boundary of the cell phase, and the phase width is about several nm to 10 nm. The platelet phase is a plate-like phase that crosses a plurality of crystal grains, and exists perpendicular to the c-axis direction of the cell phase. For this reason, platelet phases are observed in parallel within one domain. Each phase is also characteristic in terms of composition, the cell wall phase has a Cu concentration several times higher than the cell phase (main phase), and the platelet phase has a concentration of an element M such as Zr relative to the cell phase (main phase). Is several times higher. For example, in a sample in which the cell phase Cu concentration is about 3 atomic% and the Zr concentration is about 1.5 atomic%, the cell wall phase Cu concentration is about 20 atomic% and the platelet phase Zr The concentration is about 4.5 atomic%.

  In this embodiment, the Sm—Co magnet is composed of a main phase (cell phase) composed of 2-17 phase, a grain boundary phase (cell wall phase) composed of 1-5 phase and the like, and a crystal phase or amorphous other than platelet phase. A phase may be included. As other phases, an M rich phase in which the concentration of the element M is higher than that of the cell phase, a compound phase mainly composed of the elements R and Fe, and the like can be considered, but the amount is preferably about the amount of the impurity phase. It is preferable that the metal structure constituting the permanent magnet of the embodiment is substantially composed of a cell phase, a cell wall phase, and a platelet phase.

  The composition of the permanent magnet of this embodiment can be measured by ICP (Inductively Coupled Plasma) emission spectroscopy. In addition, the volume ratio of each phase is comprehensively determined using observations with an electron microscope or an optical microscope, X-ray diffraction, etc., but a transmission electron micrograph of a permanent magnet cross-section (hard magnetization axis plane) is taken. It can be determined by area analysis. As the cross section of the permanent magnet, a cross section substantially in the center of the surface having the maximum area of the product surface is used.

The domain wall energy of the 1-5 phase (cell wall phase) precipitated at the grain boundary of the 2-17 phase (cell phase) is larger than the domain wall energy of the 2-17 phase, and this domain wall energy difference is a barrier for domain wall movement. It becomes. In the Sm ₂ Co ₁₇ type magnet, it is considered that the domain wall pinning type coercive force is expressed by the 1-5 phase having a large domain wall energy acting as a pinning site. Here, it is considered that the domain wall energy difference is mainly caused by the Cu concentration difference. If the Cu concentration in the cell wall phase is higher than the Cu concentration in the cell phase, it is considered that coercive force appears. For this reason, it is preferable that the cell wall phase has a Cu concentration of 1.2 times or more the Cu concentration of the cell phase. Thereby, the cell wall phase can sufficiently function as a pinning site of the domain wall, and a sufficient coercive force can be obtained.

  As a typical example of the cell wall phase (grain boundary phase) existing at the grain boundary of the cell phase, the above-described 1-5 phase can be mentioned, but it is not necessarily limited thereto. When the cell wall phase has a Cu concentration of 1.2 times or more of the Cu concentration of the cell phase, the cell wall phase can sufficiently function as a pinning site of the domain wall, thereby obtaining a high coercive force. Is possible. Therefore, the cell wall phase may be a Cu-rich phase as described above. Examples of the cell wall phase other than the 1-5 phase include a 1-7 phase that is a high-temperature phase (structure before phase separation), a 1-5 phase precursor phase that occurs in the initial stage of phase separation of the 1-7 phase, and the like. Can be mentioned.

As described above, Cu is an essential element for allowing the SmCo-based magnet to exhibit a high coercive force. It is considered that Cu is enriched in the cell wall phase generated by aging treatment or the like, and the cell wall phase acts as a pinning site of the domain wall, thereby producing a coercive force. Sm—Co magnets are required to increase (BH) _max in addition to magnetization and coercive force. As described above, the factor determining the value of (BH) _max of the permanent magnet includes the squareness of the hysteresis loop in addition to the residual magnetization and the coercive force. Even if the magnet has a large residual magnetization, if the squareness is poor, the (BH) _max value becomes lower than the theoretical value expected from the magnitude of the residual magnetization.

In order to increase the magnetization of the Sm—Co magnet, it is effective to replace part of Co with Fe and increase the Fe concentration. Therefore, in the Sm-Co system of the embodiment, the Fe content is in the range of more than 30 atomic% of the total amount of elements other than the element R (Fe, Co, Cu, M) to 45 atomic% or less (0.3 < p ≦ 0.45). However, in the composition region where the Fe concentration is high, the squareness of the hysteresis loop of the Sm—Co magnet tends to deteriorate. Such deterioration of the squareness becomes a factor of decreasing the (BH) _max of the Sm—Co magnet.

  As a result of intensive studies on the cause of the deterioration of the squareness described above, the present inventors tend to cause variations in the Cu concentration of the cell wall phase in the composition region where the Fe concentration is high, and thereby the pinning potential of the domain wall is increased. It was found that a large cell wall phase and a cell wall phase with a small pinning potential occur. As described above, since the domain wall energy of the cell wall phase varies depending on the Cu concentration, the cell wall phases having greatly different Cu concentrations have different magnitudes of the pinning potential of the domain wall.

  When the pinning potential of the domain wall differs depending on the cell wall phase, there are regions where domain wall movement is easy and regions where migration is difficult. For this reason, the domain wall movement when an external magnetic field is applied may occur stepwise from the cell phase surrounded by the cell wall phase having a low Cu concentration toward the cell phase surrounded by the cell wall phase having a high Cu concentration. Become. Therefore, it is considered that the squareness of the hysteresis loop is deteriorated in the Sm—Co magnet having a composition with a high Fe concentration. In order to improve the squareness affected by the distribution of the Cu concentration in the cell wall phase, it is effective to make the spatial distribution of the Cu concentration in the cell wall phase uniform.

Therefore, in the Sm—Co magnet of this embodiment, the spatial distribution of the Cu concentration in the cell wall phase (grain boundary phase) is set to 5 or less in standard deviation. By applying a cell wall phase having such a Cu concentration spatial distribution, the squareness of the hysteresis loop of the Sm—Co magnet having a high Fe concentration can be improved. That is, while maintaining high coercivity of the Sm-Co magnet based on the high magnetization imparted to the Sm-Co magnet based on the high Fe concentration, the phase separation structure, the Cu concentration difference between the cell phase and the cell wall phase, etc. By improving the squareness of the hysteresis loop of the Sm—Co based magnet, the value of (BH) _max of the Sm—Co based magnet can be improved. Therefore, it is possible to provide a high-performance Sm—Co magnet.

Here, as an index representing the squareness, the squareness ratio is defined as follows for convenience. That is, the squareness ratio represents the ratio of the actually measured value of (BH) _{max to} the theoretical value of (BH) _max represented by the equation (2). The theoretical value of (BH) _max is a value calculated by the equation (3) from the measured value of residual magnetization (Br).
Squareness ratio = (BH) theoretical value of the measured values / (BH) _max of _{max × 100 (%) ... (} 2)
(BH) Theoretical value of _max = Br × Br / 16π × 10 ⁴ (3)

  FIG. 2 is a diagram illustrating an example of a magnetization curve of the Sm—Co based magnet of the embodiment in comparison with a conventional Sm—Co based magnet. The Sm—Co magnet of the embodiment whose magnetization curve is shown in FIG. 2 and the conventional Sm—Co magnet have the same composition, respectively, and a main phase (cell phase) composed of 2-17 phases respectively. Although the Sm-Co magnet of the embodiment has a metal structure including a grain boundary phase (cell wall phase) and a platelet phase, the spatial distribution of the Cu concentration in the grain boundary phase is 5 or less in standard deviation. On the other hand, in the conventional Sm—Co magnet, the spatial distribution of the Cu concentration in the grain boundary phase exceeds 5 in standard deviation. As is apparent from FIG. 2, it can be seen that the Sm—Co magnet of the embodiment has a good squareness of the hysteresis loop.

  The spatial distribution of Cu concentration in the cell wall phase (grain boundary phase) varies depending on heat treatment conditions such as solution treatment and aging treatment. In order to make the spatial distribution of the Cu concentration in the cell wall phase uniform, it is effective to control the processing temperature and processing time of the solution treatment, as will be described in detail later. With regard to the aging treatment, it is effective to perform a preliminary aging treatment at a temperature lower than that temperature before the main aging treatment. Furthermore, it is effective to strictly control the processing temperature, the processing time, the cooling rate after the processing of the pre-aging treatment and the main aging treatment.

  Furthermore, the squareness of the hysteresis loop of the Sm—Co magnet is also influenced by the ratio (β / α) of the M concentration (β) of the platelet phase to the M concentration (α) of the grain boundary phase. That is, the fact that the M concentration ratio (β / α) between the grain boundary phase and the platelet phase is too high means that the diffusion of the element M represented by Zr has not progressed sufficiently. In such a case, not only the composition uniformity of the element M but also the Cu composition uniformity tends to be lowered. For this reason, in order to improve the uniformity of the spatial distribution of the Cu concentration, the M concentration ratio (β / α) of the grain boundary phase and the platelet phase is preferably less than 3. However, when the M concentration ratio (β / α) between the grain boundary phase and the platelet phase becomes 1 or less, the M concentration of the platelet phase and the grain boundary phase, which originally had a high M concentration, is reversed, and the platelet phase becomes a diffusion path In order to stop functioning, it is preferable that the M concentration ratio (β / α) of the grain boundary phase and the platelet phase exceeds 1.

  The element concentration of each constituent phase described above is measured by energy dispersive X-ray analysis using a transmission electron microscope. Specific measurement methods for transmission electron microscope images and energy dispersive X-ray analysis are shown below. First, a sintered body or alloy subjected to an aging treatment, which is in a demagnetized state, is cut parallel to the easy axis of magnetization to obtain a plate sample. At that time, the sample is taken from the inside of the sintered body or alloy from the inside of 1 mm or more. Thereafter, the plate is thinned with FIB (focused ion beam) to obtain an observation sample for a transmission electron microscope. The measurement is performed with a transmission electron microscope at an accelerating voltage of 200 kV and a magnification of 100,000 times, and is adjusted so that the cellular structure can be clearly seen. In the energy dispersive X-ray analysis, the element concentration of each constituent phase is analyzed in the above field of view.

  The spatial distribution of Cu concentration in the grain boundary phase is measured as follows. First, the Cu concentration (atomic%) in the cell wall phase portion is analyzed. At that time, the center of the cell wall phase thickness is selected as the measurement location, and 10 or more locations are measured. However, the respective measurement points are selected so as to be separated from each other by 150 nm or more. A standard deviation (σ) of the Cu concentration is calculated from the measurement data.

  The ratio (β / α) of the M concentration (α) of the grain boundary phase and the M concentration (β) of the platelet phase is measured as follows. First, the M concentration (atomic%) of the cell wall phase portion is analyzed. At that time, the center of the thickness of the cell wall phase is selected as a measurement location, and 10 or more locations are measured. However, the respective measurement points are selected so as to be separated from each other by 150 nm or more. Next, the M concentration (atomic%) of the platelet phase portion is analyzed. At that time, the center of the thickness of the platelet phase is selected as a measurement location, and measurement is performed with 10 or more platelet phases observed in parallel. The average value of M concentration is calculated from the measurement data of each of the cell wall phase and the platelet phase, and these average values are set as the M concentration (α) of the grain boundary phase and the M concentration (β) of the platelet phase, respectively. The ratio (β / α) is calculated.

  The permanent magnet of this embodiment is produced as follows, for example. First, an alloy powder containing a predetermined amount of element is prepared. The alloy powder is prepared by, for example, producing a flake-like alloy ribbon by a strip casting method and then pulverizing it. In the strip casting method, it is preferable to obtain a thin ribbon that is solidified continuously to a thickness of 1 mm or less by pouring the molten alloy onto a cooling roll rotating at a peripheral speed of 0.1 to 20 m / sec. If the peripheral speed of the cooling roll is less than 0.1 m / sec, composition variations are likely to occur in the ribbon, and if the peripheral speed exceeds 20 m / sec, the crystal grains are refined to a single domain size or less, and good magnetic properties. Cannot be obtained. The peripheral speed of the cooling roll is more preferably in the range of 0.3 to 15 m / sec, and still more preferably in the range of 0.5 to 12 m / sec.

  The alloy powder may be prepared by pulverizing an alloy ingot obtained by casting a molten metal by an arc melting method or a high frequency melting method. Other methods for preparing the alloy powder include a mechanical alloying method, a mechanical grinding method, a gas atomizing method, a reduction diffusion method, and the like, and an alloy powder prepared by these methods may be used. The alloy powder thus obtained or the alloy before pulverization may be homogenized by performing a heat treatment as necessary. Flakes and ingots are pulverized using a jet mill, a ball mill or the like. The pulverization is preferably performed in an inert gas atmosphere or an organic solvent in order to prevent oxidation of the alloy powder.

  Next, an alloy powder is filled in a metal mold placed in an electromagnet or the like, and pressure forming is performed while applying a magnetic field, thereby producing a green compact with the crystal axis oriented. The green compact is sintered at a temperature of 1100 to 1300 ° C. for 0.5 to 15 hours to obtain a dense sintered body. If the sintering temperature is less than 1100 ° C., the density of the sintered body is insufficient, and if it exceeds 1300 ° C., rare earth elements such as Sm evaporate and good magnetic properties cannot be obtained. The sintering temperature is more preferably in the range of 1150 to 1250 ° C, and further preferably in the range of 1180 to 1230 ° C.

  Further, when the sintering time is less than 0.5 hours, the density of the sintered body may be non-uniform. On the other hand, if the sintering time exceeds 15 hours, rare earth elements such as Sm evaporate, and good magnetic properties cannot be obtained. The sintering time is more preferably in the range of 1 to 10 hours, still more preferably in the range of 1 to 4 hours. The green compact is preferably sintered in a vacuum or in an inert atmosphere such as argon gas in order to prevent oxidation.

  The obtained sintered body is subjected to solution treatment and aging treatment to control the crystal structure. In order to obtain the 1-7 phase which is a precursor of a phase-separated structure, the solution treatment is preferably heat-treated at a temperature in the range of 1110 to 1200 ° C. for 0.5 to 24 hours. At temperatures below 1110 ° C. and temperatures exceeding 1200 ° C., the ratio of the 1-7 phase in the sample after solution treatment is small, and good magnetic properties cannot be obtained. In addition, the concentration distribution of each element in the 1-7 phase may not be sufficiently uniform. The solution treatment temperature is more preferably in the range of 1120 to 1180 ° C, still more preferably in the range of 1120 to 1170 ° C.

  When the solution treatment time is less than 0.5 hours, the constituent phases are likely to be non-uniform, and the concentration distribution of each element in the 1-7 phase may not be sufficiently uniform. Further, if the solution treatment is performed for more than 24 hours, rare magnetic elements such as Sm in the sintered body may evaporate, and thus good magnetic properties may not be obtained. The solution treatment time is more preferably in the range of 1 to 12 hours, and further preferably in the range of 1 to 8 hours. The solution treatment is preferably performed in vacuum or in an inert atmosphere such as argon gas in order to prevent oxidation.

  Next, an aging treatment is performed on the sintered body after the solution treatment. The aging treatment is a treatment for controlling the crystal structure and increasing the coercive force of the magnet. Furthermore, in order to uniformize the spatial distribution of the Cu concentration in the grain boundary phase, it is preferable to perform a preliminary aging treatment (first aging treatment) at a lower temperature before the main aging treatment (second aging treatment). The first aging treatment is preferably held at a temperature of 500 to 900 ° C. for 0.5 to 10 hours, and then slowly cooled to a temperature of 20 to 450 ° C. at a cooling rate of 0.1 to 5 ° C./min. By performing the first aging treatment under such conditions, the spatial distribution of the Cu concentration in the grain boundary phase can be made uniform. Further, the M concentration ratio (β / α) between the grain boundary phase and the platelet phase can be controlled within a favorable range.

  In the second aging treatment, after holding at a temperature of 700 to 900 ° C. for 10 to 100 hours, it is gradually cooled to a temperature of 20 to 600 ° C. at a cooling rate of 0.1 to 5 ° C./min, and subsequently cooled to room temperature. It is preferable. By performing the second aging treatment under such conditions, it becomes possible to improve the coercive force and the like of the Sm—Co magnet having a phase separated structure. The treatment temperature T2 of the second aging treatment is preferably set higher than the treatment temperature T1 of the first aging treatment (T2> T1), whereby the spatial distribution of the Cu concentration in the grain boundary phase can be made uniform. The aging treatment is preferably performed in vacuum or in an inert gas atmosphere such as argon gas in order to prevent oxidation.

  When the first aging treatment temperature is less than 500 ° C. or exceeds 900 ° C., the coercive force may be lowered or the squareness may be deteriorated. The first aging treatment temperature is more preferably 600 to 850 ° C., further preferably 700 to 850. When the first aging treatment time is less than 0.5 hours, the coercive force may be lowered and the squareness may be deteriorated. On the other hand, when the first aging treatment time exceeds 10 hours, the productivity is lowered and the cost is increased. The first aging treatment time is more preferably 1 to 5 hours.

  Further, when the cooling rate after the first aging heat treatment is less than 0.1 ° C./min, the productivity is lowered and the cost is increased. If the cooling rate after the first aging heat treatment exceeds 5 ° C./min, the squareness may be deteriorated. The cooling rate after the first aging heat treatment is more preferably in the range of 0.5 to 4 ° C./min, and still more preferably in the range of 1 to 3 ° C./min.

  When the second aging treatment temperature is less than 700 ° C. or exceeds 900 ° C., a homogeneous mixed structure of the cell phase and the cell wall phase cannot be obtained, and the magnetic characteristics of the permanent magnet may be deteriorated. The aging treatment temperature is more preferably 750 to 880 ° C, and further preferably 780 to 850 ° C. When the second aging treatment time is less than 10 hours, the cell wall phase may not be sufficiently precipitated from the 1-7 phase. On the other hand, when the retention time exceeds 100 hours, the cell wall volume increases in thickness, and the volume fraction of the cell phase decreases, or the crystal grains become coarse, resulting in good magnet characteristics. May not be obtained. The second aging treatment time is more preferably 10 to 90 hours, and further preferably 20 to 80 hours.

  Further, when the cooling rate after the second aging heat treatment is less than 0.1 ° C./min, the productivity is lowered and the cost is increased. If the cooling rate after the second aging heat treatment exceeds 5 ° C./min, a homogeneous mixed structure of the cell phase and the cell wall phase cannot be obtained, and the magnetic properties of the permanent magnet may be deteriorated. The cooling rate after the second aging heat treatment is more preferably in the range of 0.3 to 4 ° C./min, and further preferably in the range of 0.5 to 3 ° C./min.

  This permanent magnet can be used for various motors and generators. Further, it can be used as a fixed magnet or a variable magnet of a variable magnetic flux motor or a variable magnetic flux generator. Various motors and generators are configured by using the permanent magnet of this embodiment. When the permanent magnet of this embodiment is applied to a variable magnetic flux motor, the technology disclosed in Japanese Patent Application Laid-Open Nos. 2008-29148 and 2008-43172 is applied to the configuration and drive system of the variable magnetic flux motor. be able to.

  Next, the motor and the generator of the embodiment will be described with reference to the drawings. FIG. 3 shows a permanent magnet motor according to the embodiment. In the permanent magnet motor 1 shown in FIG. 3, a rotor (rotor) 3 is disposed in a stator (stator) 2. In the iron core 4 of the rotor 3, the permanent magnet 5 of the embodiment is arranged. Based on the characteristics of the permanent magnet according to the embodiment, the permanent magnet motor 1 can be improved in efficiency, size, cost, and the like.

  FIG. 4 shows a variable magnetic flux motor according to the embodiment. In the variable magnetic flux motor 11 shown in FIG. 4, a rotor (rotor) 13 is disposed in a stator (stator) 12. In the iron core 14 of the rotor 13, the permanent magnets of the embodiment are arranged as a fixed magnet 15 and a variable magnet 16. The magnetic flux density (magnetic flux amount) of the variable magnet 16 can be varied. Since the magnetization direction of the variable magnet 16 is orthogonal to the Q-axis direction, it is not affected by the Q-axis current and can be magnetized by the D-axis current. The rotor 13 is provided with a magnetized winding (not shown). By passing a current from the magnetization circuit through the magnetization winding, the magnetic field directly acts on the variable magnet 16.

  According to the permanent magnet of the embodiment, by changing the various conditions of the manufacturing method described above, for example, a fixed magnet 15 having a coercive force exceeding 500 kA / m and a variable magnet 16 having a coercive force of 500 kA / m or less are obtained. Can do. In the variable magnetic flux motor 11 shown in FIG. 4, the permanent magnet of the embodiment can be used for both the fixed magnet 15 and the variable magnet 16, but the permanent magnet of the embodiment is used for one of the magnets. It may be used. Since the variable magnetic flux motor 11 can output a large torque with a small device size, the variable magnetic flux motor 11 is suitable for a motor such as a hybrid vehicle or an electric vehicle that requires high output and miniaturization of the motor.

  FIG. 5 shows a generator according to the embodiment. A generator 21 shown in FIG. 5 includes a stator (stator) 22 using the permanent magnet of the embodiment. A rotor (rotor) 23 disposed inside the stator (stator) 22 is connected to a turbine 24 provided at one end of the generator 21 via a shaft 25. The turbine 24 is rotated by fluid supplied from the outside, for example. Note that the shaft 25 can be rotated by transmitting dynamic rotation such as regenerative energy of an automobile instead of the turbine 24 rotated by a fluid. Various known configurations can be employed for the stator 22 and the rotor 23.

  The shaft 25 is in contact with a commutator (not shown) disposed on the side opposite to the turbine 24 with respect to the rotor 23, and an electromotive force generated by the rotation of the rotor 23 is used as an output of the generator 21 as a phase separation bus. The power is boosted to the system voltage and transmitted through a main transformer (not shown). The generator 21 may be either a normal generator or a variable magnetic flux generator. Note that the rotor 23 is charged by static electricity from the turbine 2 or a shaft current accompanying power generation. Therefore, the generator 21 is provided with a brush 26 for discharging the charge of the rotor 23.

  Next, examples and evaluation results thereof will be described.

Example 1
Each raw material was weighed so as to have the composition shown in Table 1, and then arc-melted in an Ar gas atmosphere to prepare an alloy ingot. The alloy ingot was coarsely pulverized by mortar pulverization and then finely pulverized by a jet mill to prepare an alloy powder having an average particle size of 5 μm. The alloy powder was pressed at a pressing pressure of 1 t in a magnetic field of 1.5 T to form a green compact, which was then held and sintered in an Ar atmosphere at 1200 ° C. for 3 hours, followed by 1170 ° C. for 3 hours. A solution treatment was performed to produce a sintered body.

  Next, the sintered body after the solution treatment was subjected to heat treatment as a first aging treatment under conditions of 780 ° C. × 3 hours, and then gradually cooled to 200 ° C. at a cooling rate of 1 ° C./min. Then, after heat-treating on the conditions of 850 degreeC x 10 hours as a 2nd aging treatment, it cooled gradually to 300 degreeC with the cooling rate of 1 degree-C / min, and also cooled to room temperature. Both the first and second aging treatments were performed in an Ar atmosphere. The sintered magnet thus obtained was subjected to the characteristic evaluation described later.

(Example 2)
Each raw material was weighed so as to have the same composition as in Example 1, and then arc-melted in an Ar gas atmosphere to prepare an alloy ingot. The alloy ingot was coarsely pulverized by mortar pulverization and finely pulverized by a jet mill to prepare an alloy powder having an average particle size of 4 μm. The alloy powder was pressed into a green compact at a press pressure of 1 t in a magnetic field of 1.5 T, then sintered by holding at 1190 ° C. for 3 hours in an Ar atmosphere, and subsequently at 1150 ° C. for 5 hours. A solution treatment was performed to produce a sintered body.

  Next, the sintered body after the solution treatment was subjected to heat treatment as a first aging treatment under conditions of 730 ° C. × 1.5 hours, and then gradually cooled to 300 ° C. at a cooling rate of 1.5 ° C./min. Subsequently, as a second aging treatment, heat treatment was performed under the condition of 850 ° C. × 15 hours, and then gradually cooled to 500 ° C. at a cooling rate of 1.5 ° C./min, and further cooled to room temperature. Both the first and second aging treatments were performed in an Ar atmosphere. The obtained sintered magnet was subjected to the characteristic evaluation described later.

(Examples 3 to 6)
Each raw material was weighed so as to have the composition shown in Table 1, and then arc-melted in an Ar gas atmosphere to prepare an alloy ingot. The obtained alloy ingot was heat-treated at 1170 ° C. for 1 hour in an Ar atmosphere, and then the alloy ingot was coarsely pulverized by mortar pulverization and further finely pulverized by a ball mill to prepare an alloy powder having an average particle diameter of 4 μm. The alloy powder was pressed into a green compact at a press pressure of 1 t in a magnetic field of 1.5 T. The green compact was sintered at 1190 ° C. for 3 hours in an Ar atmosphere, followed by solution treatment at 1150 ° C. for 3 hours to produce a sintered body.

  Next, the sintered body after the solution treatment was subjected to heat treatment as a first aging treatment under conditions of 720 ° C. × 2 hours, and then gradually cooled to 200 ° C. at a cooling rate of 1.5 ° C./min. Subsequently, as a second aging treatment, heat treatment was performed under conditions of 810 ° C. × 50 hours, and then gradually cooled to 400 ° C. at a cooling rate of 1 ° C./min, and further cooled to room temperature. Both the first and second aging treatments were performed in an Ar atmosphere. The sintered magnet thus obtained was subjected to the characteristic evaluation described later.

(Examples 7 to 9)
Each raw material was weighed so as to have the composition shown in Table 1, and then arc-melted in an Ar gas atmosphere to prepare an alloy ingot. The alloy ingot was loaded into a quartz nozzle and melted by high-frequency induction heating, and then the molten metal was poured into a cooling roll rotating at a peripheral speed of 0.6 m / second and continuously solidified to produce an alloy ribbon. The alloy ribbon was coarsely pulverized and then finely pulverized by a jet mill to prepare an alloy powder having an average particle size of 4 μm. The alloy powder was pressed into a green compact at a press pressure of 1 t in a magnetic field of 1.5 T. The green compact was sintered at 1200 ° C. for 1 hour in an Ar atmosphere and subsequently subjected to a solution treatment at 1170 ° C. for 10 hours to produce a sintered body.

  Next, the sintered body after the solution treatment was subjected to heat treatment as a first aging treatment under conditions of 750 ° C. × 2 hours, and then gradually cooled to 200 ° C. at a cooling rate of 1.5 ° C./min. Then, after heat-treating on the conditions of 850 degreeC x 10 hours as a 2nd aging treatment, it cooled gradually to 600 degreeC with the cooling rate of 1 degree-C / min, and also cooled to room temperature. Both the first and second aging treatments were performed in an Ar atmosphere. The sintered magnet thus obtained was subjected to the characteristic evaluation described later.

(Comparative Example 1)
A green compact was produced under the same conditions as in Example 1, using an alloy powder having the same composition as in Example 1. The green compact was sintered in an Ar atmosphere at 1220 ° C. for 3 hours and subsequently subjected to solution treatment at 1180 ° C. for 8 hours to produce a sintered body. Next, the sintered body after the solution treatment was subjected to a heat treatment as a first aging treatment under conditions of 780 ° C. × 10 hours, and then gradually cooled to 300 ° C. at a cooling rate of 7 ° C./min. Subsequently, heat treatment was performed as a second aging treatment under the conditions of 850 ° C. × 5 hours, and then gradually cooled to 400 ° C. at a cooling rate of 0.5 ° C./min, and further cooled to room temperature. Both the first and second aging treatments were performed in an Ar atmosphere. The sintered magnet thus obtained was subjected to the characteristic evaluation described later.

(Comparative Example 2)
A green compact was produced under the same conditions as in Example 1 using an alloy powder having the same composition as in Example 2. The green compact was sintered in an Ar atmosphere at 1220 ° C. for 1 hour, and subsequently subjected to a solution treatment at 1210 ° C. for 8 hours to produce a sintered body. Next, the sintered body after the solution treatment was subjected to heat treatment as a first aging treatment under conditions of 800 ° C. × 8 hours, and then gradually cooled to 200 ° C. at a cooling rate of 7 ° C./min. Then, after heat-treating on condition of 840 degreeC x 3 hours as a 2nd aging treatment, it cooled gradually to 400 degreeC with the cooling rate of 5 degreeC / min, and also cooled to room temperature. Both the first and second aging treatments were performed in an Ar atmosphere. The sintered magnet thus obtained was subjected to the characteristic evaluation described later.

(Comparative Examples 3 to 9)
A green compact was produced under the same conditions as in Examples 3 to 9, using an alloy powder having the same composition as in Examples 3 to 9. The green compact was sintered in an Ar atmosphere at 1220 ° C. for 3 hours, followed by solution treatment at 1210 ° C. for 2 hours to produce a sintered body. Next, the sintered body after the solution treatment was subjected to heat treatment as a first aging treatment under conditions of 400 ° C. × 7 hours, and then gradually cooled to 200 ° C. at a cooling rate of 3 ° C./min. Then, after heat-treating on condition of 850 degreeC x 5 hours as a 2nd aging treatment, it cooled gradually to 600 degreeC with the cooling rate of 5 degreeC / min, and also cooled to room temperature. Both the first and second aging treatments were performed in an Ar atmosphere. The sintered magnet thus obtained was subjected to the characteristic evaluation described later.

The metal structures of the sintered magnets of Examples 1 to 9 and Comparative Examples 1 to 9 described above were observed with TEM. As a result, it was confirmed that all had a 2-17 phase (cell phase), a grain boundary phase (cell wall phase), and a platelet phase. Moreover, it was confirmed that the grain boundary phase has a Cu concentration of 1.2 times or more with respect to the 2-17 phase. Based on the method described above, the standard deviation of the Cu concentration spatial distribution in the grain boundary phase and the M concentration ratio (β / α) of the grain boundary phase and the platelet phase were determined. These results are shown in Table 2. Next, the magnetic characteristics of each sintered magnet were evaluated with a BH tracer, and residual magnetization, coercive force, and (BH) _max were measured. Furthermore, the squareness ratio was obtained from the measured residual magnetization and the measured value of (BH) _max based on the method described above. Table 2 shows the squareness ratio of each example.

As is clear from Table 2, it can be seen that the sintered magnets of Examples 1 to 9 all have a high squareness ratio. On the other hand, the permanent magnets of Comparative Examples 1 to 9 do not have a sufficient squareness ratio because the standard deviation of the spatial distribution of Cu concentration in the grain boundary phase is low. Moreover, the residual magnetization was 1.14 to 1.20 T in Examples 1 to 5 and Comparative Examples 1 to 5, and 1.16 to 1.23 T in Examples 6 to 9 and Comparative Examples 6 to 9. The coercive force is 1100 to 2000 kA / m in Examples 1 to 5, 800 to 1500 kA / m in Examples 6 to 9, 800 to 2000 kA / m in Comparative Examples 1 to 5, and 500 to 1500 kA / m in Comparative Examples 6 to 9. Met. It was confirmed that the (BH) _max value of the permanent magnets of Comparative Examples 1 to 9 was lower than the theoretical value expected from the magnitude of the residual magnetization. As a result, the permanent magnet of this embodiment is suitable for a motor or a generator, and the motor or the generator can be used for an automobile or the like.

  In addition, although several embodiment of this invention was described, these embodiment is shown as an example and is not intending limiting the range of invention. These novel embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.

  DESCRIPTION OF SYMBOLS 1 ... Permanent magnet motor, 2 ... Stator, 3 ... Rotor, 4 ... Iron core, 5 ... Permanent magnet, 11 ... Variable magnetic flux motor, 12 ... Stator, 13 ... Rotor, 14 ... Iron core, 15 ... Fixed magnet, 16 ... Variable magnet , 21 ... variable magnetic flux generator, 22 ... stator, 23 ... rotor, 24 ... turbine, 25 ... shaft, 26 ... brush.

Claims (9)

_{Formula: R (Fe p M q Cu} r Co 1-pqr) z
(Wherein R represents at least one element selected from Sm, Ce, Nd, Pr and Y, M represents at least one element selected from Ti, Zr and Hf, and 50 atomic% or more is Zr) , P, q, r and z are atomic ratios of 0.3 <p ≦ 0.45, 0.01 ≦ q ≦ 0.05, 0.01 ≦ r ≦ 0.1, 5.6 ≦ z ≦, respectively. 9)
A motor comprising a permanent magnet having a composition represented by:
The permanent magnet has a metal structure including a Th ₂ Zn ₁₇ type crystal phase, a grain boundary phase, and a platelet phase, and has a squareness ratio of 87% or more,
A motor in which the ratio (β / α) of the concentration of the element M (β) in the platelet phase to the concentration (α) of the element M in the grain boundary phase is in the range of more than 1 and less than 3. The motor according to claim 1, wherein
The permanent magnet is a motor used for at least one of a fixed magnet and a variable magnet. The motor according to claim 1 or 2,
A motor comprising: a stator; and a rotor disposed inside the stator and having the permanent magnet. _{Formula: R (Fe p M q Cu} r Co 1-pqr) z
(Wherein R represents at least one element selected from Sm, Ce, Nd, Pr and Y, M represents at least one element selected from Ti, Zr and Hf, and 50 atomic% or more is Zr) , P, q, r and z are atomic ratios of 0.3 <p ≦ 0.45, 0.01 ≦ q ≦ 0.05, 0.01 ≦ r ≦ 0.1, 5.6 ≦ z ≦, respectively. 9)
A generator comprising a permanent magnet having a composition represented by:
The permanent magnet has a metal structure including a Th ₂ Zn ₁₇ type crystal phase, a grain boundary phase, and a platelet phase, and has a squareness ratio of 87% or more,
The generator in which the ratio (β / α) of the concentration of the element M (β) in the platelet phase to the concentration (α) of the element M in the grain boundary phase is in the range of more than 1 and less than 3. The generator according to claim 4,
The permanent magnet is a generator used for at least one of a fixed magnet and a variable magnet. The generator according to claim 4 or 5,
A generator comprising: a stator; and a rotor disposed inside the stator and having the permanent magnet. The generator according to any one of claims 4 to 6,
A generator connected to a turbine provided at one end of the generator via a shaft.   An automobile comprising the motor according to any one of claims 1 to 3 or the generator according to any one of claims 4 to 7. The automobile according to claim 8,
An automobile in which dynamic rotation of the automobile is transmitted to a shaft provided at one end of the generator.