JPH04343203A - Production of permanent magnet powder - Google Patents

Abstract

PURPOSE:To provide a production method for ultramicroscopic crystal magnet powder, which can be handled easily, having the coercive force of 6kOe or higher in an R-T-N permanent magnet. CONSTITUTION:An H2-removing heat treatment is conducted on coarsely pulverized powder in a single H2 gas or an inert gas (excluding N2 gas) and H2 gas mixed atmosphere, and the powder having the aggregate structure of 0.05 to 0.5mum in average crystal particle diameter in the coarsely pulverized state. The handling of powder in the succeeding process becomes very easy, the powder and a high coercive force magnet can be obtained by bringing into a magnetic state by conducting a nitriding treatment.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] This invention is a permanent magnet powder for bonded magnets and sintered magnets of R (rare earth element)-T (iron group element)-N system having high coercive force used in various motors, actuators, etc. According to the production method, this coarsely pulverized powder is subjected to heat treatment in H2 gas alone or in a mixture with inert gas (excluding N2 gas), and H2 removal treatment by heating and holding in a predetermined atmosphere to form fine crystal grains. The present invention relates to a method for producing permanent magnet powder that is easy to handle and has a high coercive force by forming a textured powder having a diameter and then nitriding the powder.

0002

BACKGROUND OF THE INVENTION Magnet powders having an ultrafine structure obtained by ultra-quenching, mechanical alloying, etc. have been used as Nd--Fe--B permanent magnet powders.

[0003] Nd-Fe-B powder for permanent magnets has a low Curie point (Tc) of around 300°C and a large temperature coefficient of Br and iHc, so by increasing Tc by adding Co etc. Although it is possible to increase Br
The temperature coefficient α was limited to about -0.08/deg at most.

[0004]Recently, R2Fe17 compounds have become nearly twice as high in absolute temperature by absorbing N2;
It is 160℃ higher than Tc of d-Fe-B system, and S
It has been reported that m2Fe17 nitride provides an anisotropic magnetic field that exceeds the anisotropy of R2Fe14B.

[0005]

[Problems to be Solved by the Invention] The Sm2Fe17 nitride does not have the iHc that is practically required in the normal manufacturing method.
It is not possible to produce magnet powder that yields 6 kOe or more, and the required ultrafine crystal magnet powder can only be obtained by special manufacturing methods such as mechanical alloying, which poses problems in mass production on an industrial scale. .

[0006] In addition, the nitriding reaction to obtain Sm2Fe17 nitride has a slow reaction rate, so unless the raw material powder is pulverized to 10 μm or less before the nitriding process, the N atoms will not diffuse into the interior of the powder. Moreover, the finely pulverized powder of 10 μm or less is difficult to handle in the subsequent process, and unless extreme care is taken, it may catch fire or easily oxidize, resulting in deterioration of properties and even corrosion.

[0007] The present invention provides a permanent magnet in which an ultrafine crystalline powder for a magnet that can obtain a coercive force of 6 kOe or more can be easily produced in an R-T-N system permanent magnet, and the powder can be easily handled thereafter. The purpose is to provide a method for producing powder.

[0008]

[Means for Solving the Problems] This invention provides R 9 to
12 at% (R: at least one rare earth element and S
Contains 30% or more of m), T 88-91 at% (T:
An ingot consisting of Fe or a part of Fe replaced with 50% or less Co or Ni) is coarsely pulverized or heated at 800°C to 12°C.
After performing solution treatment at 00°C for 1 hour to 100 hours to reduce the primary crystal phase of Fe groups contained in the metal structure to 20 vol% or less, coarse pulverization is performed to obtain coarsely pulverized powder with an average particle size of 50 to 500 μm. After that, the coarsely pulverized powder was heated to 0.1 to 10 atm.
(converted to room temperature) in H2 gas or an inert gas (excluding N2 gas) with an equivalent H2 partial pressure (however, the total pressure is 10 atm or less in terms of room temperature) at 500 to 900℃.
Heated and held for 0 minutes to 8 hours, and further increased the H2 partial pressure to 1 x 10-2
H2 removal treatment is performed by holding at 500 to 900°C for 30 minutes to 8 hours in a vacuum of Torr or less or in a mixture with an inert gas excluding N2, and the average crystal grain size is 0.05 to 0.5.
A powder having a texture of μm is prepared, and then the powder is N
2 Pressure (normal temperature) 35 in N2 gas of 0.5 to 50 atm
After holding at 0 to 650°C for 30 minutes to 6 hours, cooling
R 9-12 at%, T 88-91 at%, N
This is a method for producing permanent magnet powder, characterized by obtaining permanent magnet powder containing 9.5 to 13.6 at% and having high coercive force.

[0009]

[Operation] This invention provides an R-T-N permanent magnet,
As a result of various studies with the aim of manufacturing a powder for magnets made of ultrafine crystals that is easy to handle and has a coercive force of 6 kOe or more, the R-T-N compound represented by Sm2Fe17N2 The parent RT compound is about 0.
It was discovered that powder for R-T-N permanent magnets with high coercive force could be obtained by nitriding the powder having a microcrystalline texture with a single magnetic domain particle critical diameter of 3 μm. Completed the invention.

That is, the inventors conducted R-T in H2 gas.
When the alloy is heated, the R-T compound becomes RH2■3 and αFe
The same R-T as before is obtained by further decomposing H2
Furthermore, by controlling the temperature and holding time of heating in H2 gas and H2 removal treatment, the crystal grain size of the generated RT compound can be controlled, and by subsequent nitriding treatment, high storage stability can be achieved. It has been found that an R-T-N permanent magnet powder having an ultrafine structure that exhibits magnetic force can be obtained.

[0011] Furthermore, not only R2Fe17 compounds but also
As mentioned above, rare earth compounds of iron group elements are
It was discovered that by performing heating in two gases and H2 removal treatment, an ultrafine crystal texture could be obtained, and that the magnetic properties could be controlled by the subsequent N2 diffusion treatment. The R-T-N based permanent magnet powder according to the present invention has an average crystal grain size of 0.05 to 0.5 μm as a coarsely pulverized powder with a required average grain size.
This has the advantage that not only can a coercive force of 6 kOe or more be obtained, but also that handling of the powder in subsequent steps is extremely easy.

Reasons for limiting manufacturing conditions The present invention is characterized in that a coarsely pulverized powder of a required particle size can be obtained as an aggregate of fine crystal structures without changing its size in appearance, and this point is different from the conventional H2 This method is essentially different from the occlusion pulverization method. In addition to the conventional mechanical crushing method and gas atomization method, the method of coarsely pulverizing the starting raw material is H2
Coarse pulverization may be carried out by the occlusion pulverization method.To simplify the process, this coarse pulverization method by H2 occlusion and the heat treatment in H2 gas for ultrafine crystallization according to the present invention are combined, and the process is continuously carried out in the same equipment. It is also preferable to adopt a method of treating In this invention, the average particle size of the coarsely pulverized powder is 50 to 500.
The reason why it is limited to μm is that if it is less than 50 μm, there is a risk of magnetic deterioration due to oxidation of the powder, and if it exceeds 500 μm, it will take a long time for the nitriding treatment, which is undesirable.

[0013] In the present invention, when heating with H2 gas alone or in a mixture with inert gas (excluding N2 gas), if the H2 partial pressure is less than 0.1 atm (converted to room temperature), the above-mentioned decomposition and production will be insufficient. No effect can be obtained, and if it exceeds 10 atm, the processing equipment becomes too large, which is not preferable in terms of industrial production costs, so the H2 partial pressure is set to 0.1 to 10 atm. A more preferable range is 0.5 to 1.5 atm. Further, when using a mixture of an inert gas other than N2 gas and H2 gas at the above H2 partial pressure, the maximum pressure is set to 10 atm or less for the same reason.

[0014] The heat treatment temperature in H2 gas alone or in a mixture of inert gas (excluding N2 gas) and H2 gas is:
Below 500°C, the RT compound only absorbs H2,
Decomposition into RH2■3 and αFe etc. is not carried out, and 900
If the temperature exceeds .degree. C., RH2 and 3 will become unstable and the product will grow into grains, making it difficult to form an RT compound with an ultrafine structure after dehydrogenation. Further, in order to sufficiently carry out the above-mentioned decomposition reaction, it is necessary to hold the heat treatment for 30 minutes to 8 hours.

[0015] In the present invention, if the temperature of the H2 removal process of H2 gas is less than 500°C, decomposition of RH2-3 will not proceed, and if it exceeds 900°C, grain growth will result in a coarse structure.
500 to 900℃ because excellent high coercive force cannot be obtained.
The range shall be . Further, in order to sufficiently carry out the above-mentioned decomposition reaction, it is necessary to hold the heat treatment for 30 minutes to 8 hours.

[0016] The H2 partial pressure during the H2 removal process is 1×10-2
If it exceeds Torr, the processing will take a long time and is not preferable, so it is set to 1×10 −2 Torr or less. If the H2 partial pressure is within this range, this treatment may be carried out in an inert gas other than N2 gas, which eliminates the need for vacuum container equipment that can withstand high pressure, which simplifies the equipment and is economical.

[0017] The average crystal grain size of the powder after H2 removal treatment is 0.
The reason why crystals are limited to 0.05 to 0.5 μm is that crystals smaller than 0.05 μm are practically difficult to form, and even if crystals smaller than 0.05 μm are obtained, there is no advantage in terms of properties.
This is because if it exceeds m, the single magnetic domain particle critical diameter becomes larger and the coercive force of the powder decreases, making it undesirable as a powder for permanent magnets.

The reason why the temperature during nitriding treatment was limited to 350 to 650°C is that nitriding does not proceed below 350°C.
This is because if the temperature exceeds 0° C., RN is generated and the RT compound is decomposed, leading to deterioration of magnetic properties. The holding time during the nitriding treatment is set to 30 minutes to 6 hours, since sufficient nitriding will not proceed if it is less than 30 minutes, and decomposition will occur if it exceeds 6 hours, resulting in deterioration of the magnetic properties.

[0019] N2 pressure (room temperature) during nitriding treatment is 0.5~
The reason for limiting the pressure to 50 atm is that if it is less than 0.5 atm, the nitriding reaction rate is slow, and if the pressure is increased, the reaction will proceed quickly, but if it exceeds 50 atm, the processing equipment will become too large, which is not desirable in terms of industrial production costs. It is.

[0020] In this invention, it is necessary that the metal structure of the coarsely pulverized alloy powder, which is the starting material, is substantially occupied by the R2T17 compound, and α-Fe, Fe-Co, and Fe-Ni crystals crystallize as primary crystals. The remaining amount of alloy is 20vo overall
It is preferably 1% or less. Since the primary phase does not contain the R element as a component, it is not changed by the H2 treatment, and its magnetic properties do not change even in the subsequent N2 treatment and remain as a soft magnetic layer, so the obtained powder The magnetic properties of will deteriorate. Therefore, the amount of primary crystal phases such as α-Fe needs to be kept below 20% by volume, and for this purpose solution treatment is performed in vacuum or in an inert gas excluding N2 gas. If solution treatment is carried out at a temperature below 800°C, a sufficient diffusion reaction will not proceed and it will take a long time for the primary crystal phase to disappear. At a temperature above 1200°C, rapid solution treatment is possible, but the essential components will be removed. In addition to evaporating Sm, which causes a composition shift, the chemical reactivity of the alloy increases, which adversely affects the alloy container and the furnace wall.
The solution treatment temperature is 800°C to 1200°C. In the composition range of this invention, the primary phase is an alloy phase that does not substantially contain R, but the amount of this alloy phase decreases with the solution treatment time, and the rate of decrease is dependent on the temperature. The rate increases as the temperature increases, but even when the solution treatment temperature is 1200°C, the amount of primary crystal phase cannot be reduced to 20% or less by volume unless solution treatment is performed for at least 1 hour, and the processing temperature is 800°C.
Even when the diffusion rate is slow, 100 hours or less is sufficient to reduce the amount of primary crystal phase to 20% or less by volume, and no further solution treatment is necessary.

Reasons for limiting the powder composition In the powder composition of the present invention, the rare earth element R is Y, La
, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho,
It includes Er, Tm, and Lu, contains one or more of these, and contains at least 30% or more of Sm relative to R, and in some cases, Sm may account for 100% of R. The reason why Sm accounts for 30% or more of R is that if Sm is less than 30%, the uniaxial anisotropy weakens and the coercive force decreases. If R is less than 9 at%, the coercive force will decrease due to the precipitation of Fe, and if it exceeds 12 at%, other compounds with low coercive force and low Curie point will be generated and the magnetic properties will deteriorate, so R should be 9 to 12 at%. shall be.

[0022] The iron group element T includes at least one of Fe, Co, and Ni, and it is important that Fe is contained in an amount of 50% or more of T. That is, if the Fe content in T is less than 50%, the cost increases and the magnetization decreases, which is not preferable. T
is less than 88 at%, R other than Sm2Fe17 compound
A rich phase appears, the coercive force and Curie point decrease, and 90
If it exceeds at%, the coercive force decreases due to α-Fe precipitation, so it is set to 88 to 91 at%.

[0023] Furthermore, the N contained in the powder after nitriding treatment is
If it is less than 9.5 at%, the Curie point and coercive force are not much different from the original Sm2Fe17 compound, and if it exceeds 13.6 at%, the R2Fe17NX compound will decompose due to the precipitation of the RN compound, which is undesirable. .6a
It is assumed to be t%.

[0024]

【Example】

Example No. 1 shown in Table 1 obtained by melting in a high frequency melting furnace. 1
After coarsely pulverizing the ingot having a composition of 7 to 7 with a stamp mill in an Ar gas atmosphere to an average particle size of 100 μm, the coarsely pulverized powder was pulverized in H2 gas with a H2 partial pressure of 10 atm (normal temperature equivalent).
After heating to 00℃ and holding for 2 hours, the H2 partial pressure becomes 1×10
A dehydrogenation treatment was performed at 800° C. for 1 hour in an atmosphere of −4 Torr to obtain a powder having a texture with an average crystal grain size shown in Table 1. Thereafter, it was subjected to nitriding treatment at 450 DEG C. for 2 hours in N2 gas with a N2 partial pressure of 10 atm, and then cooled to obtain R-T-N magnet powder having the properties shown in Table 1. In Table 1,
α is the temperature coefficient of Br at 20°C to 120°C.

[0025] After mixing 2.0 wt% epoxy resin with R-T-N magnet powder, 3.0 wt% epoxy resin was mixed in a magnetic field of 10 kOe.
Compression molded at a pressure of ton/cm2 and further heated to a temperature of 150°C.
A bonded magnet was produced by curing the resin at ℃ for 30 minutes. Table 2 shows the magnetic properties of the obtained bonded magnet.

Comparative Example Composition No. 1 in Table 1 Using the same coarsely pulverized powder as in 1, it was held in H2 gas with a H2 partial pressure of 2.0 atm (normal temperature equivalent) for 2 hours, and then heated after exhausting the excess H2 gas.
De-H2 at 0℃, 2 hours, H2 partial pressure 1 x 10-4 Torr
After processing, a ground powder was obtained. Table 1 shows the average grain size at this time.
Shown below. Furthermore, Table 1 shows the properties of the R-T-N magnet powder after it was subjected to the same nitriding treatment as in the example. Thereafter, a bonded magnet was produced under the same conditions as in the example, and its magnetic properties are shown in Table 2.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

Effects of the Invention The R-T-N permanent magnet powder according to the present invention can be obtained by heating coarsely pulverized R-T powder in H2 gas alone or in a mixture with an inert gas (excluding N2 gas); A deH2 treatment is carried out by heating and holding in a predetermined atmosphere, and the average crystal grain size is 0.05 to 0.05% while the coarsely pulverized powder has the required average grain size.
The powder can be made into a powder having a texture of 5 μm, which makes handling of the powder extremely easy in the subsequent process, and after that, by nitriding, a coercive force of 6 kOe or more can be obtained, as is clear from the examples.

Claims (2)

[Claims] [Claim 1] R 9 to 12 at% (R: at least one rare earth element and containing 30% or more of Sm), T
After coarsely pulverizing an ingot consisting of 88 to 91 at% (T: Fe or a part of Fe replaced with 50% or less of Co or Ni) to a coarsely pulverized powder with an average particle size of 50 to 500 μm, The coarsely ground powder is 0.1 to 10 atm (converted to room temperature)
of H2 gas or an inert gas (excluding N2 gas) with an equivalent H2 partial pressure (however, the total pressure is 1 at room temperature).
H2 removal by heating and holding at 500 to 900°C for 30 minutes to 8 hours at 0 atm or less, and then holding at 500 to 900°C for 30 minutes to 8 hours at a H2 partial pressure of 1 x 10-2 Torr or less.
The powder was treated to have a texture with an average grain size of 0.05 to 0.5 μm, and then the powder was heated under N2 pressure (
room temperature) 350-65 in N2 gas of 0.5-50 atm
A method for producing permanent magnet powder, which comprises maintaining the powder at 0° C. for 30 minutes to 6 hours and then cooling it. 2. The ingot is subjected to solution treatment at 800° C. to 1200° C. for 1 hour to 100 hours to reduce the Fe-based primary crystal phase contained in the metal structure to 20 vol% or less, and then coarsely pulverized. The method for producing permanent magnet powder according to claim 1, characterized in that: