Grain boundary engineering of sintered magnetic alloys and compositions derived therefrom.

Abstract

To provide a permanent magnet with improved magnetic properties and a method for manufacturing the same.SOLUTION: A method includes homogenizing a first population of particles of a first GBM alloy with a second population of particles of a second core alloy to form a composite alloy preform. The first GBM alloy is represented by the formula: ACbRxCoyCudMz, and the second core alloy is represented by the formula: G2Fe14B. The method also includes heating the composite alloy preform particles to form a population of mixed alloy particles, compressing the mixed alloy particles to form a green compact under an inert atmosphere and a magnetic field of suitable strength to align the magnetic particles in a common direction of magnetization, and sintering the green compact and annealing the sintered compact.SELECTED DRAWING: Figure 4A

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application is a continuation of U.S. patent application Ser. No. 62 / 288,243 filed on January 28, 2016, and U.S. patent application Ser. No. 62 / 288,243 filed on April 28, 2016. The present application claims the benefit of priority to U.S. Patent Application No. 62 / 324,501, filed on the 19th, which states: All are incorporated herein by reference for all purposes.

[0002] (Technical field) The present disclosure relates to a method for producing rare earth-based permanent magnets and the improved magnets resulting therefrom. The present invention is directed to magnets having magnetic properties. Particular embodiments include grain boundary engineered NdFe1 Included are alloys including neodymium-iron-boron magnets, including 4B magnets. [Background technology]

[0003] (background) Neodymium, iron, boron (NdFeB) magnets were first developed in the early 1980s and are now the most widely manufactured. These magnets are used in MRI machines, hard disk drives, and other electronic devices. Disk drives, speakers, linear motors, A / C motors, wind turbines, hybrids electric vehicles, elevator motors, and mobile phones, as well as other household appliances Widely used in a wide range of applications. However, rare earth elements are required for enhanced magnetic performance. In particular, supplies of dysprosium (Dy) and terbium (Tb) are insufficient. Global demand often exceeds supply, especially as many mines are subject to export quotas. Therefore, they are located in China, which prevents free trade of these elements and drives up prices. This limited supply of rare earth elements is a concern for industries in many developed economies. Currently, about 40% of sintered magnets weigh about 100-200 grams or more each. In the automotive industry, it is incorporated into hybrid electric motors as a magnetic segment Therefore, the minimum concentration of heavy rare earth elements (e.g., Dy and Tb) is used, and still produce NdFeB magnets and other rare earth-containing magnets suitable for use in electric motors. It is desirable.

[0004] Conventional NdFeB material manufacturing produces sintered NdFeB magnets with high coercivity that can operate at high temperatures. To form the main body, a high concentration of Dy or Tb element is required. The method has high associated material and process costs.

[0005] A process for manufacturing magnetic materials by combining two types of alloys using powder mixing technology is known. However, such processes typically involve the use of two species, both of which contain Dy. There are high production costs associated with producing similar alloys. Quality control is also difficult due to the inconsistent mixing of powders. Another attempt to increase the magnet strength is to add high concentrations of Dy, Tb, or other heavy elements to the surface of the magnet body. Pre-sintered rare earth magnets are laminated, sputtered, or coated with a material that During the subsequent heating process, these heavy elements are converted into magnets. Diffuses from one side / edge of the body through grain boundaries into the body, changing the properties of the magnet; The coercive force is increased without affecting the magnetic properties, making the process suitable for motor applications. It is said to reduce the amount of Dy or Tb required to make a high-coercivity magnet. However, such grain boundary diffusion is limited to magnets with body thicknesses not exceeding 6 mm, and Successful implementation requires additional post-processing steps and complex and expensive machinery. In addition, such a diffusion process limits the extent to which the coercivity can be increased; Typically, only a 30-40% increase in coercivity is achieved using this process.

[0006] The present disclosure is directed to solving at least some of these problems. Summary of the Invention

[0007] (overview) The present disclosure provides a method for making useful rare earth magnets that can operate at high temperatures, and the resulting The magnets produced are described.

[0008] Some embodiments involve multiple methods for producing sintered magnetic bodies with improved coercivity and remanence. A method, each method comprising: (a) A first population of particles of a first grain boundary modified (GBM) alloy is combined with a second population of particles of a second core alloy. The weight ratio of the first and second populations of particles is homogenized within a range of about 0.1:99.9 to about 16.5:83.5. forming a composite alloy preform; The second core alloy is substantially of the formula GFe 14 B (wherein G is a rare earth element) Optionally, the second core alloy may be made of a non-ferrous or recycled material. doped with one or more transition metal elements or main group elements; The first population of particles of the first GBM alloy has an average particle size in the range of about 1 micron to about 4 microns. Within the perimeter; The second population of particles of the second core alloy has an average particle size of about 2 microns to about 5 microns. the homogenizing is within the range; and (b) heating the composite alloy preform to a temperature above the solidus temperature of the first alloy but below the solidus temperature of the second core alloy; Heating to a temperature below the melting point of gold to form a population of discrete mixed alloy particles In some embodiments, the mixed alloy particles are particles a cellular coating (i.e., in the composite alloy preform), or a continuous or semi-continuous coating. as a coating on the first The GBM alloy coating may be characterized as a second core alloy particle.

[0009] In another embodiment, the first GBM or the second GBM is homogenized prior to the homogenizing step (a). Coarse grains of either the core alloy or both the first GBM and second core alloy are Treat with hydrogen gas under conditions and for a time sufficient to allow absorption of hydrogen into one or both of the materials. The hydrogen treatment step may be followed by a degassing treatment step.

[0010] In yet another embodiment, the method further comprises: (c) mixing the population of mixed alloy particles with the magnetic particles in the presence of a magnetic field of sufficient strength to align the magnetizations in a common direction, preferably in an inert atmosphere. The method further includes compressing the powders together in air to form a green compact.

[0011] An additional embodiment is (d) sintering the green compact into a sintered body comprising core-shell grains and a grain boundary composition. and subjecting the mixture to at least one temperature within the range of about 800°C to about 1500°C for a time sufficient to sinter the mixture to a temperature of about 1500°C. The method further comprises heating the powder compact.

[0012] In yet another embodiment, the method further comprises (e) cycling between vacuum and inert gas environments. The method further comprises heat treating (or annealing) the sintered body. In some embodiments, the temperature of the cycling environment is in the range of about 450°C to about 600°C. .

[0013] In another embodiment, during and / or after sintering and / or during annealing or thereafter, (f) the sintering body / sintered body is converted into a final residue, as described herein. Applying a magnetic field of sufficient strength to achieve magnetic retention and coercivity, e.g., about 400 kA / m It is magnetized by using a magnetic field in the range of about 1200 kA / m (0.5 to 1.5 T).

[0014] In some of these embodiments, the first GBM alloy is substantially or as a coating on said second core alloy particle, b R x Co y Cu d M z (In the formula, (A) AC contains Nd and Pr in an atomic ratio within the range of 0:100 to 100:0, and b is about 5 atomic % to about 6 atomic %. a value in the range of 5 atomic percent; (B) R is one or more rare earth elements, and x is a value within the range of about 5 atomic % to about 75 atomic %. and; (C) Co is cobalt and Cu is copper; (D) y is a value within the range of about 20 atomic % to about 60 atomic %; (E) d is a value in the range of about 0.01 atomic % to about 12 atomic %; (F) M is at least one transition metal element other than Cu and Co, and z is about 0.01 atomic % a value in the range of about 18 atomic percent; and (G) b, x, y, d, and z are independently variable within their stated ranges, provided that: The sum of b+x+y+d+z is greater than 95, 96, 97, 98, 99, 99.5, 99.8, or 99.9 atomic % and is less than about 99.9 (up to 100 atomic % or 100 atomic %) It is expressed as:

[0015] In some other of these embodiments, the first GBM alloy has a structure substantially of the formula Nd j Dy k Co m Cu n Fe p (In the formula, j is 1-2, 2-3, 3-4, 4-5, 5-6, 6-7, 7-8, 8-9, 9-10, 10 for all compositions ~11, 11~12, 12~13, 13~14, 14~15, 15~16, 16~17, 17~18, 18~19, 19~20 atoms %, or a range inclusive of two or more of these ranges; k is 1-5, 5-10, 10-15, 15-20, 20-25, 25-30, 30-35, 35- 40, 40 to 45, 45 to 50, 50 to 55, 55 to 60 atomic %, or two or more of these ranges in atomic percent within the inclusive range; m is 1-5, 5-10, 10-15, 15-20, 20-25, 25-30, 30-35, 35- 40, 40 to 45, 45 to 50, 50 to 55, 55 to 60 atomic %, or two or more of these ranges in atomic percent within the inclusive range; n is 0.1-0.5, 0.5-1, 1-1.5, 1.5-2, 2-2.5, 2.5-3, 3-3.5 for all compositions , 3.5~4, 4~4.5, 4.5~5, 5~5.5, 5.5~6, 6~6.5, 6.5~7, 7~7.5, 7.5~8, 8.5~9 , 9 to 9.5, 9.5 to 10, 10 to 12, 12 to 14, 14 to 16, 16 to 18, 18 to 20 atomic %, or the atomic percentage being within a range inclusive of two or more of the ranges; p is 1-2, 2-3, 3-4, 4-5, 5-6, 6-7, 7-8, 8-9, 9-10, 10 for all compositions ~11, 11~12, 12~13, 13~14, 14~15, 15~16, 16~17, 17~18, 18~19, 19~20 atoms %, or a range inclusive of two or more of these ranges; or t j, k, m, n, and p are independently variable within their stated ranges, provided that j+k The sum of m, n, and p is greater than 95, 96, 97, 98, 99, 99.5, 99.8, or 99.9 atomic percent, and is about 99.9 atomic percent. % or up to 100 atomic % It is expressed as:

[0016] The present disclosure is not limited to methods of processing, and in some embodiments, the disclosed methods Particles, green compacts, or sintered bodies produced by the method, and articles and devices comprising these sintered bodies Provides services.

[0017] Yet another embodiment provides a composition comprising a GBM alloy, wherein the alloy comprises substantially , formula:AC b R x Co y Cu d M z (In the formula: (A) AC contains Nd and Pr in an atomic ratio within the range of 0:100 to 100:0, and b is about 5 atomic % to about 6 atomic %. 5 atomic % or a value in the range of 10 atomic % to about 50 atomic %; (B) R is one or more rare earth elements, and x is a value within the range of about 10 atomic % to about 60 atomic %. and; (C) Co is cobalt and Cu is copper; (D) y is a value within the range of about 30 atomic % to about 40 atomic %; (E) d is a value in the range of about 0.01 atomic % to about 6 atomic %; (F) M is at least one transition metal element other than Cu and Co, and z is about 0.01 atomic % a value in the range of about 10 atomic percent; and (G) The sum of b+x+y+d+z is one of 95, 96, 97, 98, 99, 99.5, 99.8, or 99.9 atomic percent (More than 100 atomic % and not more than 100 atomic %) and wherein the composition contains less than 0.1% by weight of oxygen or carbon.

[0018] GBM alloys are amorphous or contain columnar and spherical crystallites. The mixture may contain more than one phase.

[0019] The present disclosure also provides an apparatus for mixing particles, comprising: (a) an adiabatic rotary reactor, the reactor having an inlet port and an outlet port, each Ports are adapted to add and remove particles from the rotary reactor, respectively. Each inlet port and outlet port is optionally fitted with a particle sieve. Thermal rotary reactor; (b) a vacuum source capable of providing a vacuum to the adiabatic rotary reactor; (c) a heater capable of heating the rotary reactor during use; and optionally (d) a sampling portal that allows for the collection of samples while the device is in operation; The apparatus is described, comprising:

[0020] The present disclosure also provides a method for processing the inventive method and composition, including an apparatus for mixing the particles. 1. A system for: (a) subjecting the magnetic material to a pressure in the range of about 1 to about 10 bar (or higher in some circumstances); Rotary hydrogen reactor capable of processing with hydrogen; (b) a rotary degassing chamber that is evacuated and heated and capable of degassing hydrogen-containing magnetic materials; bar; (c) Jet mill equipment; (d) Approximately 800~3000kN (20cm 2 Ability to apply forces in the range of 60 MPa (or 60 MPa) to a group of particles a compressing device having a force, the compressing device being configured to apply the pressure to the a magnetic field capable of providing a magnetic field in the range of about 0.2 T to about 2.5 T while applying the particle population; the compression device having a source attached thereto; and (e) a sintering chamber, providing the chamber with an internal temperature in the range of about 400°C to 1200°C; while providing selective vacuum and inert atmosphere environments within the chamber. and the sintering chamber. In this embodiment, the system comprises any two, three, four, or five of elements (a) through (e). Prepare. [Brief explanation of the drawings]

[0021] BRIEF DESCRIPTION OF THE DRAWINGS This application will be better understood when read in conjunction with the accompanying drawings, in which: For this reason, the drawings show exemplary embodiments of the subject matter; however, each is not intended to be limiting unless the present invention is specifically illustrated. While representing embodiments of the disclosure, the presently disclosed subject matter is not limited to the specific methods, devices, and methods disclosed. The drawings are not necessarily drawn to scale. In the drawing:

[0022] [Figure 1]FIG. 1 shows a theorized schematic of one embodiment of a GBE-NdFeB-based microstructure comprising multiple shells surrounding a GFeB (where G is a rare earth element, e.g., Nd)-based hard magnetic phase.

[0023] [Figure 2] FIG. 2 shows some physical forms of GBM alloy materials: (A) shows the morphology of the GBM alloy, and (B) shows an example of a strip cast flake.

[0024] [Figure 3] FIG. 3 shows one exemplary process flow diagram highlighting various options for producing grain boundary modifications (GBM alloys) and various processing steps that can be used to add the GBM alloys to a strip cast foil to create an exemplary GBE-NdFeB magnet.

[0025] [Figure 4] Figures 4A-4B show two demagnetization loops of a conventionally sintered strip cast magnet and a GBE-NdFeB magnet, referred to as the magnet and the GBE magnet, respectively. In Figure 4A, the weight ratio is S1 (97.7):A2 (2.3). See Table 2. In Figure 4B, the weight ratio is S1 (97.2):A1 (2.8).

[0026] [Figure 5] Figure 5 shows a backscattered SEM image of a GBM alloy based on the following composition in atomic percent: Nd 8.93%, Pr 3.05%, Dy 21.13%, Tb 21.60%, Co 38.33%, Cu 5.33%, Fe 1.28%, and Zr 0.62%; the different contrast levels indicate that the GBM alloy consists of multiple phases. See Table 10 for a description of Phases 1, 2, and 3.

[0027] [Figure 6] FIG. 6 shows an exemplary powder XRD pattern of a representative first GBM alloy (see, e.g., Table 3).

[0028] [Figure 7] FIG. 7 shows an exemplary powder XRD pattern of a representative second GBM alloy (see, e.g., Table 4). DETAILED DESCRIPTION OF THE INVENTION

[0029] DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS The present invention relates to methods or processes for processing magnetic materials and to methods or processes for processing these materials. The resulting composition is directed to: In some embodiments, the first GBM alloy is a second GBM alloy; In some embodiments, to achieve this, The process involves reducing the size of the first GBM and the second core particle to a specific dimension. The size of the micro-grains of the second core (magnetic) alloy is then coated with particles of the first GBM alloy. suitable for mixing (or more generally blending) with Subsequent processing involves powder metallurgy, where elements of the first GBM alloy are converted to the second GBM alloy by heat treatment. Conditions are provided that allow diffusion of 2 into the grains of the core alloy, resulting in a core-shell structure. wherein the core contains and maintains the hard magnetic phase of the second core alloy. Curing and further heat treatment allows for additional control of the magnetic properties of the resulting sintered body. Using the methods described herein, low levels of expensive rare elements are used in their production. High, uniform coercive force with improved thermal stability and resistance to demagnetizing and corrosion It is possible to manufacture high energy rare earth magnets, including GBE-NdFeB magnets, having

[0030] The present invention may be practiced in conjunction with the accompanying drawings and examples, all of which form a part of this disclosure. This can be more readily understood by reference to the following description, which is to be understood as follows: You are not limited to the specific products, methods, conditions, or parameters described or shown in the document. and the terminology used herein is intended to describe particular embodiments by way of example only. It should be understood that no limitation of any claimed invention is intended. Likewise, unless otherwise specified, no possible mechanism, mode, or theory or direction of action is implied. Any description of the above reasons is intended to be exemplary only and is not intended to be limiting of the invention herein. The disclosure does not include any such proposed mechanism, mode, or theory of action or reason for improvement. Throughout this document, statements are made as follows: It is recognized that the disclosure refers to compositions and methods of making and using the compositions. Describe or claim features or embodiments relating to the composition or to methods of making or using the composition. If so required, such description or claim in a given context may be deemed to be a representation of those features or embodiments. In all other of these contexts (i.e., compositions, methods of making, and methods of using), It is recognized that the present invention is intended to extend to embodiments in which:

[0031] In this disclosure, the singular forms "a," "an," and "the" refer to plural References to numbers, and to specific numerical values, are and includes at least the specified value. Thus, for example, reference to "a material" includes and at least one of such materials and their equivalents known to those skilled in the art. do.

[0032] When values ​​are expressed as approximations, by use of the descriptor "about," it is understood that the particular value may vary depending on the embodiment. It will be understood that, in general, the use of the term "about" is intended to provide a general understanding of the disclosed subject matter. The approximate values ​​used are shown, which may vary depending on the desired properties to be obtained by the problem. It should be interpreted based on its function in a specific context. In some cases, the value used for a particular The number of significant figures listed may be one non-limiting way of determining the scope of the term "about." In other cases, the step numbers used for a series of values ​​may be used in conjunction with the term "about" for each value. Possible intended ranges may be determined. All ranges, if any, are inclusive. and are combinable, i.e., reference to values ​​stated in multiple ranges means that the values ​​within those ranges Includes all values ​​of

[0033] Certain features of the invention that are, for clarity, described herein in the context of separate embodiments, may also be combined into a single It should be appreciated that these may be provided in combination within a single embodiment. Unless incompatible with or specifically excluded from the scope of any other and such combinations may be combined with other embodiments. To the contrary, for the sake of brevity, the description may be made in the context of a single embodiment. The various features of the invention described may be provided separately or in any subcombination. Later, embodiments may be described as part of a series of steps or as part of a more general structure. However, each of the steps can be combined with another and can be implemented independently. For example, in steps (a) to (f) of the method described herein, steps Each of steps (a), (b), (c), (d), (e), and (f), and any combination of two or more of these steps. are considered separate embodiments of the present disclosure.

[0034] Any theory or means of operation is intended to be illustrative of the concepts or features of the invention(s). It is intended only to help visualize certain aspects and is not guaranteed to occur with any particular certainty. Therefore, we have provided some information to help you understand the concept. Although the present invention(s) may be implemented in accordance with any particular theory of operability described herein, It should be recognized that the accuracy of the

[0035] The transitional phrases "comprising" and "consisting essentially of" "Partially of" and "consisting of" are terms used in patent terminology. acular) generally accepted meaning; i.e., (i) "including / comprising" "containing," "containing," or "characterized" "comprising" is a synonym for "by" and is inclusive, i.e., open. (ii) is a general description of the invention and does not exclude additional unrecited elements or method steps; "Consisting of" does not include any element, step, or ingredient not specified in the claim. and (iii) "consisting essentially of" excludes any part or all of the components of a claim that are not expressly stated. "materials or processes" and "materials or processes that substantially affect the basic and novel feature(s) of the claimed invention" The phrase "including / having" is intended to imply a limitation to "things that have no effect on the An embodiment described in terms of "can be" (or its equivalent) may also be described as an embodiment in terms of "from" (or its equivalent). The term "essentially consisting of" also provides for what is independently described in terms of "consisting of" and "consisting essentially of." These embodiments, which are provided from the perspective of "essentially consisting of," are fundamental and novel. The feature(s) may be used or include the materials described in these embodiments. (or the magnetic material itself), but still, the resulting material Impurities that have little or no additional or detrimental effect on magnetic properties The optional presence of cellulose or other additives is permitted.

[0036] Where a list is presented, unless otherwise stated, each individual element of the list and It should be understood that all combinations of the above are separate embodiments. For example, "A, B, The list of embodiments provided as "A or C" may also refer to embodiments "A," "B," "C," "A if or B," "A or C," "B or C," or "A, B, or C." Furthermore, when a broad genus (or a list of elements within that genus) is described, It is understood that separate embodiments are also provided for the specific exclusion of one or more members of the genus. For example, a reference to the genus "rare earth elements" should be , Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) It is intended to include not only any one or combination of the following but also to specifically exclude each member of the genus. Even if not specifically recited, specific embodiments may include one or more members of the genus. Also includes general genera not including the above (e.g., Sm).

[0037] Throughout this specification, words are referred to by their symbols as would be understood by one of ordinary skill in the art. However, to avoid misunderstandings, the meaning of certain terms should be To specifically define or clarify a taste.

[0038] As used herein, the term "NdFeB" refers to a composition containing neodymium, iron, and boron. At least part of it is stoichiometric Nd2Fe 14 B. In addition, the term "GBE-NdFeB" refers to a "grain boundary engineered composition" ("GBE composition") that is intended to provide a "grain boundary engineered composition." Nd produced by so-called grain boundary engineering ("GBE"), which incorporates grain boundary modifiers ("GBM"), 2Fe 14 In this context, GBE or grain boundary engineering refers to compositions containing B (or "NdFeB"). Particulate alloys described as modifier (or modified) alloys (or "GBM alloys"), including NdFeB The particles, and structures produced from such particles, are characterized in that the particular metal associated with the particulate alloy , in the NdFeB particle body, forming a matrix for the grains when sintered together. and react to form a "GBE magnet" ("grain boundary engineered magnet"). This GBM alloy metal migration into the NdFeB particles results in the core-shell If the particles are, for example, as shown in FIG. 1; i.e., the original NdFe 14 B particle core and core-shell can be characterized as containing gradients of various alloying metals distributed throughout the particle. These concepts are described more fully elsewhere herein. It will be published.

[0039] The terms "GBM" and "GBE" are used interchangeably because they refer to the same principle of modifying the grain boundaries of sintered bodies. Any substitution of one word for the other should not be construed as a significant difference in meaning.

[0040] As used herein, the term "homogenizing" refers to the preparation of a uniform distribution of particles. It refers to the process of mixing under suitable conditions to result in a "substantially homogeneous" composition. The process of densification also results in the attrition of some or all of the particles. Although homogenization (pure uniformity) may be the desired goal, the term "homogenizing" does not necessarily mean However, this does not result in perfect uniformity. Reflecting the observations, the resulting composition was sampled in at least three samples, e.g. For example, if the sample is tested by ICP and the results of the three analyses are within a certain target accuracy range (e.g. For example, the standard deviation of the measurements of the material from the mean is less than 5, 3, 2, 1, 0.5, or 0.1%, preferably or less than 0.5 or 0.1%, or 0.1% to 0.5% of the target value for that ingredient It may be considered "substantially homogeneous" if it is within the range of 1 / 2.

[0041] As used herein, the term "solidus temperature" refers to the temperature below which a substance becomes completely solid. It provides its usual meaning of being a body (crystallizing).

[0042] The term "substantially represented by formula X" refers to an alloy having the nominal formula X, but containing low levels of The presence of impurities or intentionally added dopants is permitted.

[0043] The term "mixed alloy" as in "mixed alloy particles" refers to a mixture of a second core alloy and a second alloy. The particles are in contact with, and preferably at least partially contact with, particles of the first GBM alloy. The composition of the first GBM alloy depends on the heat treatment the mixed alloy has undergone. Some of the elements may be diffused into the grains of the second core alloy, while others may not be diffused at all. Sometimes there isn't

[0044] "Compact" has its ordinary connotation in the context of a pre-sintered body.

[0045] Within the context of sintered bodies, the terms "grain" or "grain body" have their usual connotations in that context. Has.

[0046] Where a range is provided, every integer or tenth of an integer within that range is an integer equal to any independent integer within that same range. For example, "5 to 10 atoms" is intended to represent the endpoint (either minimum or maximum) of a given %, 10-15 atomic %, 15-20 atomic %, 20-25 atomic %, 25-30 atomic %, 30-35 atomic %, 35-40 atomic%, 40-45 atomic%, 45-50 atomic%, 50-55 atomic%, 55-60 atomic%, 60-65 atomic%, 65 % or less, 70 to 75 atomic %, or any combination of two or more of these ranges." The ranges represented by the formula (I) are also intended to be illustrative and not restrictive, and other embodiments may be embodied in a range of 5-6, 6-7, 7-8, 8-9, 9-10 atoms...70 up to 71, 71 to 72, 73 to 74, 75 atomic %, or any combination of two or more of these ranges " is intended to include those also represented as ".

[0047] The term "is / is more than at least one of (a set of values)" (e.g., "However, Nd+Pr+D The total amount of y+Tb exceeds at least one of 95, 98, 99, 99.5, 99.8, or 99.9 atomic %. The "may" is not intended to imply that each value in the series is an independent embodiment. Furthermore, when the sum of the values ​​is stated as exceeding one or more values ​​(e.g., "95, 98, 99, 99.5, 99.8, or 99.9 atomic % or more) It is clear that the content of the cations in the cations does not exceed 100 atomic percent. The statement "at least one of the following exceeds 99.9 atomic percent" also applies to the total of 95-98, 98-99, and 99-9 9.5, 99.5 to 99.8, 99.8 to 99.9, 99.9 to 100 atomic %, or two or more of these ranges Any nominal deviation from 100%. impurities or other significant impurities, including those from main group elements such as Al, C, Si, N, O, or P. This can be attributed to the dopants added diagrammatically.

[0048] Unless otherwise specified, percentages are given in atomic % (or mole %). Atomic % may also be given in terms of its decimal equivalent. For example, the composition (Nd 0.01-0. 18 Pr 0.01-0.18 Dy 0.3-0.5 Tb 0.3-0.5 ) aa (Co 0.85-0.95 Cu 0.04-0.15 Fe 0.01-0.08 ) bb (Zr 0.00-1 .00 ) cc In the term Nd 0.01-0.18 and Pr 0.01-0.18 These elements are present in an amount of 1 to 18 atomic percent. The term Dy refers to the presence of 0.3-0.5 and Tb 0.3-0.5 These elements are 30 to 50 atoms It means that it exists within the range of %.

[0049] "Optional" or "optionally" means that the situation described after it may or may not occur. so that the description will identify embodiments in which the situation occurs and instances in which it does not occur. It means to include.

[0050] The present disclosure relates to bulk, and grain or intragranular compositions for homogeneous or substantially homogeneous alloys. It refers to the chemical composition of both the powder and the composition within or across the grain boundaries. In this context, the embodiments describing these compositions may be used without regard to the quality or suitability of these compositions. implicitly describes the method used to measure the property, e.g., the whole of the alloy or particle When specific chemical compositions are described, the described embodiments may be used in conjunction with, for example, inductively coupled plasma ("I The composition may be read as the composition specified by any appropriate method, including the "CP" ("Chemical Product"). When an embodiment describes a composition within a grain or grain or grain boundary, the embodiment may be referred to as a composition within the grain, grain, or grain boundary. Energy dispersive X-ray analysis ("EDS") maps across fractured or polished surfaces, including grain boundaries. This can be read as the composition being identified or characterized using a matching technique. In such cases, the samples were polished to 1200°C with SiC before placing them in the SEM for EDS analysis. It may be prepared for analysis by (gently) polishing the surface(s) with paper. Alternatively, the surface(s) may be polished with diamond paste and rinsed. Once in the SEM, the surface was then immersed in water to ensure a clean and oxygen-free surface prior to EDS analysis. It may be cleaned or purified with Ga ions.

[0051] Various embodiments of the present disclosure provide for producing sintered magnetic bodies with improved coercivity and remanence. A plurality of methods, each method comprising: (a) combining a first population of particles of a first GBM alloy with a second population of particles of a second core alloy; The weight ratio of the first and second populations is in the range of about 0.1:99.9 to about 16.5:83.5, and the mixture is homogenized. An alloy preform (i.e., 1 to 16.5 parts first GBM alloy: 99.9 to 83.5 parts second alloy) is formed. To achieve; (i) the first GBM alloy has a composition substantially of the formula: AC b R x Co y Cu d M z (In the formula, (A) AC contains Nd and Pr in an atomic ratio within the range of 0:100 to 100:0, and b is about 5 atomic % a value in the range of ∼65 atomic %; (B) R is one or more rare earth elements, and x is in the range of about 5 atomic % to about 75 atomic %. is the value of; (C) Co is cobalt and Cu is copper; (D) y is a value within the range of about 20 atomic % to about 60 atomic %; (F)d is a value in the range of about 0.01 atomic % to about 12 atomic %; (G) M is at least one transition metal element excluding Cu and Co, and z is about 0.01 atom. % to about 18 atomic %; and (H) The sum of b+x+y+d+z is greater than 95 atomic %, or is 95, 98, 99, 99.5, 99.8, or 99.9 atomic %. % up to about 99.9 or 100 atomic % and typically the first GBM alloy contains less than 0.1 wt. % oxygen or carbon; (ii) the second core alloy is substantially GFe 14 B (wherein G is a rare earth element) and the second core alloy optionally contains one or more transition metal elements or main group elements (referred to herein as the homogenizing step is doped with a crystalline solid (further defined in (b) heating the composite alloy preform to a temperature above the solidus temperature of the first alloy but below the solidus temperature of the second core alloy; Heating to a temperature below the melting point of gold to form a population of discrete mixed alloy particles thing The method includes the method comprising:

[0052] Another embodiment provides methods for producing sintered magnetic bodies with improved coercivity and remanence. A method, each method comprising: (a) A first population of particles of a first grain boundary modified (GBM) alloy is combined with a second population of particles of a second core alloy. The weight ratio of the first and second populations of particles is homogenized within a range of about 0.1:99.9 to about 16.5:83.5. forming a composite alloy preform; The second core alloy is substantially of the formula GFe 14 B (wherein G is a rare earth element, for example, Nd) Optionally, the second core alloy is represented by (resulting from the use of virgin or recycled materials); doped with one or more transition metal elements or main group elements (to allow the use of materials the law of nature; The first population of particles of the first GBM alloy has an average particle size in the range of 1 micron to about 4 microns. Within the perimeter; The second population of particles of the second core alloy has an average particle size of about 2 microns to about 5 microns. the homogenizing is within the range; and (b) heating the composite alloy preform to a temperature above the solidus temperature of the first alloy but below the solidus temperature of the second core alloy; Heating to a temperature below the melting point of gold to form a population of discrete mixed alloy particles thing The method includes:

[0053] In some of these embodiments, the mixed alloy particles are coated with a particulate coating (such as i.e., in the composite alloy preform) or as a continuous or semi-continuous (individually separated) The first GBM alloy coating is present either as a coating (in separate mixed alloy particles). In some embodiments, the second core alloy particle may be characterized as having a fin. The first GBM alloy coating was applied in the following ranges: 0.05-0.1, 0.1-0.15, 0.15-0.2, 0.2-0.25, 0. 25 to 0.3, 0.3 to 0.35, 0.35 to 0.4, 0.4 to 0.45, 0.45 to 0.5 microns, or any of these ranges Combinations of two or more of the ranges; for example, a coating of 0.1 to 0.25 microns It has a thickness.

[0054] Although the present disclosure is made in terms of first GBM and second core alloys, individual representative or Nothing prevents the further addition of additional populations of transition or rare earth element particles. contemplates these as further embodiments.

[0055] In another embodiment, the first GBM or the second GBM is homogenized prior to the homogenizing step (a). Coarse grains of either the core alloy or both the first GBM and the second core alloy are or the hydrogen into either the first GBM or the second core alloy, or into both the first GBM and the second core alloy. Such an embodiment is characterized in that the cellulose is treated with hydrogen under conditions and for a time sufficient to allow absorption of the cellulose. This allows for the use of any conveniently produced alloy form, whether in large particle or flake form. do.

[0056] In yet another embodiment, the method further comprises independently: (c) subjecting the population of mixed alloy particles to In an inert atmosphere, a magnetic field of sufficient strength to align the magnetic particles in a common direction of magnetization is applied. (d) compressing the compact into sintered core-shell particles and grains; At least 1000°C in the range of about 800°C to about 1500°C for a time sufficient to sinter the composite into a sintered body containing the composite. (e) optionally, heating the powder compact to at least one temperature in the presence of a magnetic field; The sintered body is then heat treated (or annealed) in a vacuum and inert gas environment. This includes:

[0057] The methods currently known in the art for providing such mixed metal systems are illustrated. By significant improvement, the disclosed method specifically incorporates the use of a plurality of metals mixed with particles of a second core alloy. This provides a more uniform and evenly distributed mixture of individual, separated alloy particles. For example, the first GBM alloy may contain at least three, four, five, six, or more rare earth or Including transition metals, providing for stoichiometrically exact addition of these metals to the second core alloy. This is considerably easier to use than adding separate powders for each individual element. This provides a fast and reproducible means of adding such materials.

[0058] The method relies on an intimate metallurgical blend of the initial particles to produce a mixed alloy (pre-sintered). This intimate blend provides superior particle size reduction using less expensive additives. This provides the ability to produce substantially uniformly constructed sintered bodies of superior performance.

[0059] To help visualize the various terms, and to illustrate how certain embodiments may be applied to grain boundary compositions, Thus, a sintered body is provided that includes core-shell grains embedded or held together. In this context, the first GBM alloy may be considered a grain boundary material precursor (e.g., a GBM alloy The second core alloy was then added to the core-shell particle precursor (the gold eventually forms the grain boundary material). (e.g., at least a portion of the second core alloy may ultimately be (It forms the core of the NdFe 14 B represents one convenient embodiment of the second core alloy. In either case, the disclosure should not be limited to these representative examples or descriptions. These characterizations do not limit the compositions to these uses. Through the process described and claimed in the present application, the two alloys interact to form a target The target sintered structure is formed.

[0060] Production of the inventive powder

[0061] In some embodiments, the GBM alloy is induction cast, strip cast, or powder atomized. Similarly, the second core compound may be prepared by a method including the method described in the Examples. Gold is, in some implementations, obtained by conventional strip casting or by the addition of existing rare earth gold. It is a hard magnetic alloy produced by recycling metal magnets. are combined as non-oxides in the alloy and the reaction is carried out in the substantial absence of oxygen. (i.e., by processing the alloy under an inert atmosphere, takes careful measures to avoid the introduction of oxygen. The first GBM is capable of forming an alloy or intermetallic compound with both the first and second core alloys. The alloy should consist of a combination of AC, R, Co, Cu, and M in the proportions stated. It should also be clear that typically the first GBM alloy is thicker than the second core alloy. It is more brittle than cellulose, which is typically much harder, allowing for the necessary processing. The first GBM alloy has a lower melting point than the second core alloy, or at least It is more susceptible to migration of that element into the core alloy than vice versa.

[0062] Prior to the homogenizing step (a), either the first GBM or the second core alloy or the first GBM The coarse particles of both the first GBM alloy and the second core alloy are then heated in the presence of hydrogen. The absorption of hydrogen into either the first GBM alloy or both the first GBM alloy and the second core alloy is The method is described in terms of pretreatment under conditions and times that allow such hydrogen The treatment involves subjecting each alloy(s) to a pressure of 0.1 bar to 150 bar, preferably 1 bar to 10 bar. This may include treating the pulverized ... The term is defined by a point of any size greater than 10 microns (in any aspect direction). However, the term also applies to induction casting, strip casting, or atomization processes that produce bulk alloys. This may reflect the use of starting materials obtained from powder processes. In such cases, the process typically The material is provided in the form of flakes or pieces having centimeter-scale dimensions. In some instances, the first (GBM) slice has initial dimensions on the order of 5 cm x 5 cm x 7 cm. (See, for example, FIG. 2(A)). The second (e.g., NdFeB) flakes are obtained in a size of 0.2 cm × 2 to 10 cm. It may have initial dimensions on the order of 6 cm x 2-8 cm (see, e.g., Figure 2(B)). The thickness distribution of the strip casting section is allowed to have a standard deviation of + / - 2.5% around the mean value. Typically, the initial size of the GBM flakes is also determined by the Gaussian distribution. The method has a Gaussian distribution with an allowable variability of 5% around the method.

[0063] Following the hydrogen treatment, a degassing treatment is carried out at a temperature of, for example, about 200°C to about 850°C or about 400°C to about 600°C. This hydrogen absorption and desorption may be carried out at a temperature in the range of 1000 to 150 ... The separation cycle destabilizes the initial flakes or clumps, making them more susceptible to grinding during the homogenization step. For example, NdFeB magnets consist of two main phases. Each core grain is "coated" with a thinner layer of neodymium (Nd )-rich phase, surrounded by NdFe 14 B. This process During the process, large core phases present in the freshly strip cast NdFeB alloy were removed by A series of selective breaks into smaller crystals and / or particles without destroying the inherent magnetic potential. The hot cracking and milling process increases the surface area of ​​the core grain phase, which is typically NdF e 14 Although this results in a recovery of about 95% of the mass of B, the material is now split into a significantly increased number of very small It exists as a core or grain.

[0064] In addition to and / or supplementary to the hydrothermal cracking step(s), the homogenizing step (a) may comprise: a plurality of particles that increase the average surface area of ​​at least one, preferably both, of said particle populations; In a preferred embodiment, there are three such mixing steps. The first mixing step is used to initiate a compositional change within the mixture; the second step is used to increase the surface area. a second mixing step of uniformly distributing the first GBM alloy with the second core alloy by The third mixing step is to achieve the final target composition of the product.

[0065] Exemplary processing includes simultaneous mixing and heating to maintain particle morphology. The temperature used during mixing is periodically varied between at least a first and a second temperature. The first temperature can be varied, preferably periodically, at about ambient temperature (about 23°C). The first temperature is in the range of about 75°C to about 125°C, preferably 80°C. Conveniently, the two powders are rotated, for example, at 30 to 60 revolutions per minute, for at least 50 or 60 minutes. The mixture is mixed in a rotating mixer to produce a substantially homogeneous composition.

[0066] Examples of exemplary steps and representative methods available for use in such processes See also Figure 3 for a schematic representation.

[0067] In some embodiments, the homogenizing / mixing step comprises mixing the first and second particles as dry particles. This is achieved by tumbling in one or more rotary mixing chambers using a In an embodiment, the homogenization / mixing step is performed by grinding using grinding balls. In any case, the walls of the chamber and / or the grinding balls are sufficiently thick compared to the first and second alloy particles. The hardness should be such that the transfer of material from the former to the latter is practically non-existent. do not.

[0068] The method may take advantage of the chemical composition of the first GBM alloy and the ratio of the first GBM and second core alloys. The method is flexible in terms of both the number of usable options and the number of first GBM alloy particles. and a second population of particles of a second core alloy in a ratio of 0.1:99.9 to 99.9:0.1 to achieve the final desired composition. They may be mixed in any weight ratio combination that is consistent. In the context of the above description, the first and second The relative amounts of the alloys ranged from 0.1 parts of the first alloy per 99.9 parts of the second alloy to 83.5 parts of the second alloy per 99.9 parts of the first alloy. An additional independent embodiment may be defined as up to 16.5 parts of the first alloy. of alloy (per 100 parts of final composition), 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5. 5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 1.5, 12, 12.5, 13, 13.5, 14, 14 Increasing ratios of the first GBM alloy including 0.5, 15, 15.5, 16, or 16.5 parts of the second GBM alloy Any ratio of two of these values ​​may be used independently. An embodiment may include, for example, 6.5 parts first alloy to 93.5 parts second core alloy.

[0069] In principle, the purpose of the homogenization process is to produce a substantially homogenous mixed alloy powder with a GBM alloy grain size. The particles are then mixed with particles of a second core alloy (e.g., NdFe 14 B particles) can be "coated" To achieve this, Nd2Fe 14 Bulk cut of B and proprietary alloys Both pieces are milled to an ultra-fine particle size (approximately 3.8 micrometers).

[0070] The physical form of the first GBM alloy source material is physically different from that of the second core alloy particles. Even if large, the relative hardness and brittleness of the two materials typically determine the first GBM. The alloy grain size results in a grain size that is smaller than that of the second core alloy. In one embodiment, the first population of particles of the first GBM alloy has an average particle size of about 0.5 mm. The particle size is in the range of 100 microns to about 5 microns, or 0.5 to 0.8 microns, 0.8 to 1 micron, 1 to 2 microns. microns, 2-2.5 microns, 2.5-3 microns, 3-4 microns, or 4-5 microns Within any one or combination of subranges including, or within these ranges The range is a combination of two or more of these, for example, in the range of 1 micron to 4 microns.

[0071] In some embodiments, the average particle size of said second population of particles of said second core alloy is In some embodiments, the range is from about 2 microns to about 5 microns. , 2-2.2 microns, 2.2-2.4 microns, 2.4-2.6 microns, 2.6-2.8 microns, 2.8-3 microns Kron, 3-3.2 microns, 3.2-3.4 microns, 3.4-3.6 microns, 3.6-3.8 microns, 3. 8~4 microns, 4~4.2 microns, 4.2~4.4 microns, 4.4~4.6 microns, 4.6~4.8 microns 4.8-5 microns, 5-5.2 microns, 5.2-5.4 microns, 5.4-5.6 microns, 5.6-5.8 microns, 5.8 to 6 microns, or any combination of two or more within these ranges. The resulting mixed alloy particles may comprise a first GBM alloy particle coated with a second GBM alloy particle. Although the alloy particles may be envisioned as a core alloy particle of two, reflecting the additivity of the mixture, in some embodiments In the present invention, the average particle size of the group of individually separated mixed alloy particles is about 2 microns to about 6 microns. Preferably, the target thickness is within the range of 3 to 4 microns.

[0072] The actual morphology of the mixed alloy particles will depend on the heat treatment conditions and the specific properties of the first GBM alloy. In some cases, the first GBM alloy may simply be attached to the second core alloy, or the second The core alloy may be partially or completely coated, or the elements of the first alloy may be: The particles may begin to migrate into the second core alloy particles. may contain one or more of these types of particles.

[0073] In some embodiments, the composition of the particles involves the use of inductively coupled plasma ("ICP") During this process, the sample is typically mixed and monitored. In each case, at least three samples are taken from the chamber and tested by ICP. A sample is taken and tested, and if the results of the three analyses are within certain predetermined target ranges, Once homogenized, the particles are dispersed in a uniform mixture of the particles. using particle size analyzers available for the purpose (see, e.g., the Examples); It is also tested for proper particle size measurement. If the composition is different from the target composition, Depending on the adjustment to be made, the alloy may be adjusted by adding particles of the first or second alloy. If the particle size is too large, mixing is continued.

[0074] Powder chemistry

[0075] Processes directed to forming, sintering, and annealing of powder compacts containing mixed alloy particles Before proceeding, it is useful to describe the alloy chemistries. The following description of the grains and grain boundaries of alloy particles, compacts, and sintered bodies refers to the compositions themselves and their compositions. This applies to both methods employing the composition.

[0076] In some embodiments, the first GBM alloy is AC b R x Co y Cu d M z Including the composition stoichiometry where AC, R, M, b, x, y, d, and z are generally as described elsewhere herein. It will be apparent that this additive alloy is substantially different from the second core alloy. In some embodiments, the GBM alloy does not contain any added boron. In some embodiments, the GBM alloy does not contain any added aluminum. In yet another embodiment, the GBM alloy contains no tin. Any or all of these embodiments may contain added zinc. The situation where no Al, B, Sn, or Zn is contained means that these elements are present as inevitable impurities. Although the composition or GBE engineering may ultimately result in a Their presence is not relied upon to modify the shaped GBE magnets.

[0077] In some other embodiments, the first GBM alloy has a composition substantially of the formula Nd j Dy k Co m Cu n Fe p in where j, k, m, n, and p and their interrelationships are as defined elsewhere herein. In these embodiments, the first GBM alloy is substantially of the formula Nd j D y kCo m Cu n Fe p wherein j, k, m, n, and p and their interrelationships are The relationships are generally described elsewhere herein. and wherein the first GBM alloy contains one of the additional rare earth or transition metals as described herein. and one or more of the above, also at levels described herein.

[0078] The first GBM alloy was characterized as amorphous (no features in the XRD pattern), semi-crystalline (XRD either crystalline (showing only broadened features in the pattern) or crystalline (well-defined XRD features If crystalline, some examples may In embodiments, the morphology includes columnar and spherical crystallites.

[0079] As mentioned above, the first GBM alloy is b R x Co y Cu d M z Some experimental results, including the composition stoichiometry of In an embodiment, AC contains Nd and Pr in an atomic ratio ranging from 0:100 to 100:0 (some of the ranges are not particularly limited). The modes are 0:100, 5:95, 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50: (including 50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5, and 100:0) and b is a value within the range of about 5 atomic % to about 65 atomic %. The atomic ratio of Nd to Pr was 100:0 (i.e., Nd only), 25:75, 50:50, 75:25, or 0:100 ( Commercial sources of Nd and Pr are not available for materials with these ratios. are available, making these a convenient source for the production of GBM alloys.

[0080] The first GBM alloy was AC b R x Co y Cu d M z Yet further independent embodiments including the composition stoichiometry of In the above, b is 5 to 10 atomic %, 10 to 15 atomic %, 15 to 20 atomic %, 20 to 25 atomic %, 25 to 30 atomic %. %, 30-35 atomic %, 35-40 atomic %, 40-45 atomic %, 45-50 atomic %, 50-55 atomic %, 55- 60 atomic %, 60 to 65 atomic %, or any combination of two or more of these ranges A non-limiting exemplary range of the combination includes a range of 10 to 50 atomic percent. Embodiments include those in which ranges are defined by integer values ​​within these ranges, e.g., from about 9 to about 1. Contains 6 atomic %.

[0081] As described above, the first GBM alloy is b R x Co y Cu d M z When the composition stoichiometry of In some embodiments, R is one or more rare earth elements. The elements that make up the lanthanide and actinide series are included, but the elements that make up the lanthanide series are Elements in this series include La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, and Tb. , Dy, Ho, Er, Tm, Yb, and Lu. Various independent embodiments also include these elements. It contains any one or more of these elements, but preferably contains at least three or four of these elements. , 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 of these elements, and more preferably In additional embodiments, the present invention includes at least 6, 7, 8, 9, 10, 11, 12, 13, or 14 of the above. and R is Nd, Pr, La, Ce, Gd, Ho, Er, Yb, Dy, Tb, or two of these distinct elements. , 3, 4, 5, 6, 7, or 8, preferably at least 3, 4, 5, 6, 7, or 8 of these distinct elements. In particular embodiments, the rare earth elements are in the class of 5, 6, 7, or 8. Any one or more elements may be individually included in a subgenus or individually in a genus or subgenus. It should be recognized that Sm may be excluded from some of these combinations. In some cases, the

[0082] The first GBM alloy was AC b R x Co y Cu d M z In some embodiments, , x is a value in the range of about 5 atomic % to about 75 atomic %. In another independent embodiment, x is 5-10 atomic %, 10-15 atomic %, 15-20 atomic %, 20-25 atomic %, 25-30 atomic %, 30-35 atomic%, 35-40 atomic%, 40-45 atomic%, 45-50 atomic%, 50-55 atomic%, 55-60 atomic%, 60 up to 65 atomic %, 65 to 70 atomic %, 70 to 75 atomic %, or any two or more of these ranges Exemplary, non-limiting combination ranges are 30 to 60 atomic % or 10 to 10 atomic %. %. Another embodiment is where the range is defined by integers within these ranges. % of the total SiO 2 content, e.g., about 38 to about 48 atomic %. Again, as described elsewhere, The disclosure shows that the combination of elements is separable and that the individual elements are combinable. As just one example of this, in some embodiments, with respect to R and x, R contains at least three different rare earth elements, and the total (i.e., x) is corresponds to a value within a range, for example, from about 10 atomic % to about 60 atomic % of the first GBM alloy. .

[0083] formula AC b R x Co y Cu d M z wherein Co is present in the first GBM alloy in an amount ranging from about 20 atomic % to about 60 atomic %. In another independent embodiment, y is present in the range of 20 to 25 atomic %, 25 to 30 atomic %, 30 to 35 atomic %. atomic%, 35-40 atomic%, 40-45 atomic%, 45-50 atomic%, 50-55 atomic%, 55-60 atomic%, or is a value within any combination of two or more of these ranges; A typical combined range is 30 to 40 atomic %. In another embodiment, the range is The range is defined by an integer, for example, about 32 atomic % to about 46 atomic %. nothing.

[0084] formula AC b R x Co y Cu d M z Cu is present in the first GBM alloy in a range of about 0.01 atomic % to 15 atomic %. In an independent embodiment, d is present in the range of 0.01 to 0.05 atomic %, 0.05 to 0.1 atomic %, 0.1 to 0.15 atomic percent, 0.15 to 0.2 atomic percent, 0.2 to 0.25 atomic percent, 0.25 to 0.5 atomic percent, 0.5 to 1 atomic percent , 1-1.5 atomic %, 1.5-2 atomic %, 2-2.5 atomic %, 2.5-3 atomic %, 3-3.5 atomic %, 3.5-4 atomic % atom%, 4-4.5 atom%, 4.5-5 atom%, 5-5.5 atom%, 5.5-6 atom%, 6-7 atom%, 7-8 atom %, 8-9 atomic%, 9-10 atomic%, 10-11 atomic%, 11-12 atomic%, 12-13 atomic%, 13-14 %, 14 to 15 atomic %, or any combination of two or more of these ranges. For example, in one exemplary combination range, Cu is present in the range of 0.01 to 6 atomic %. Another embodiment is where ranges are defined by tenths of an integer value within these ranges, e.g. Examples include those with a content of about 3.1 to about 8.9 atomic %.

[0085] formula AC b R x Co y Cu d M z In the formula, M is at least one transition metal element other than Cu and Co. is present in the first GBM alloy in an amount ranging from about 0.01 atomic % to about 18 atomic %. The presence of low levels of Zr at 2500 K appears to provide the particular benefits described herein.

[0086] The group described as transition metal M includes all elements of the periodic table, except Cu and Co, which are calculated separately in the formula. Elements of groups 3 to 12 and periods 4 to 6 are included. Examples of the transition metal include Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Rh, Ir, Ni, Pd, Pt, Ag, Au Zn, Cd, and Hg. Various independent embodiments also include those containing these elements. It contains any one or more of these elements, but preferably contains at least 3, 4, 5, 6 of these elements. , 7, 8, 9, or 10 of these elements, more preferably at least 6, 7, 8, 9, In additional embodiments, M is selected from the group consisting of Ag, Au, Fe, Ga, Mo, Nb, Ni, Ti, V, In yet further embodiments, the element is W, Y, Zr, or a combination of two or more of these elements. In another embodiment, M is 1, 2, 3, 4, or 5, excluding Cu and Co. , 5, 6, 7, 8, 9, 10, 11, 12, or 13 distinct transition metal elements, preferably Cu and Co containing at least 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 distinct transition metal elements excluding As described above with respect to R, in particular embodiments, R is a group of transition metal elements. Any one or more of the elements listed may be individually included in a subgenera, or may be individually included in a genus or subgenera. It should be recognized that certain information may be excluded from the

[0087] For present purposes, this group of transition metals is considered separately in the formula of the first GBM alloy. It does not include any of the elemental lanthanide or actinide series, Cu or Co.

[0088] The first GBM alloy was AC b R x Co y Cu d M z In an independent embodiment, M is present in the first GBM alloy in a range of about 0.01 atomic % to 10 atomic %. In the formula, z is 0.01 to 0.05 atomic %, 0.05 to 0.1 atomic %, 0.1 to 0.15 atomic %, 0.15 to 0.2 atomic %. %, 0.2 to 0.25 atomic %, 0.25 to 0.5 atomic %, 0.5 to 1 atomic %, 1 to 1.5 atomic %, 1.5 to 2 atomic %, 2-2.5 atomic %, 2.5-3 atomic %, 3-3.5 atomic %, 3.5-4 atomic %, 4-4.5 atomic %, 4.5-5 atomic %, 5-5.5 atomic %, 5.5-6 atomic %, 6-7 atomic %, 7-8 atomic %, 8-9 atomic %, 9-10 atomic % , 10-11 atomic %, 11-12 atomic %, 12-13 atomic %, 13-14 atomic %, 14-15 atomic %, 15-16 atomic %, 16 to 17 atomic %, 17 to 18 atomic %, or any combination of two or more of these ranges Exemplary combination ranges include 0.01 to 10 atomic percent, 0.01 to 8 atomic percent, and 0.5 to 5 atomic percent. % or 1 to 2 atomic %. Again, for the first GBM alloy, the bicomponent of Co and Cu may be used. The amounts of y and d are considered to be within the ranges of the values ​​given for y and d, respectively. In embodiments, M (and thus the GBM alloy) does not contain any added aluminum. In an embodiment, M (and thus the GBM alloy) contains no tin. In any of these embodiments, M (and thus the GBM alloy) does not contain any zinc. Any or all of these may contain no added Al, B, Sn, or Zn. The elements may be present as unavoidable impurities, but may not necessarily be present in the composition or GBE engineering operations rely on these to modify the final molded GBE magnet. In some embodiments, the amount of Fe contained in M ​​(and thus the GBM alloy) is 0-0.5 atomic %, 0.5-1 atomic %, 1.5-2 atomic %, 2-2.5 atomic %, 2.5-3 atomic %, 3-3.5 atomic %, 3.5-4 atomic %, 4-4.5 atomic %, 4.5-5 atomic %, 5.5-6 atomic %, 6-6.5 atomic %, 6. 5 to 7 atomic %, 7 to 7.5 atomic %, 7.5 to 8 atomic %, or any two or more of these ranges The combination is, for example, in the range of 0.5 to 4 atomic %.

[0089] In the formula provided for the first GBM alloy, in some embodiments, b+x+y+d+z The sum is greater than 95 atomic percent. In some preferred embodiments, the sum is greater than 98, 99, 99 %. More than one or more of 99.5, 99.8, or 99.9 atomic %, and most preferably up to 99.9 atomic %. or nearly 100 atomic percent. Any deviation from 100 atomic percent is Incidental impurities introduced into the alloy or from the raw materials used to make the alloy. or reflects the intentional addition of other elements, such as main group elements of the periodic table. The elements may include, for example, Al, C, Si, N, O, and P. Typically, the first GBM alloy has a 0. Contains less than 1% by weight of oxygen or carbon.

[0090] Within the more general definition of the first GBM alloy formula, certain elemental compositions are preferred. For example, in some embodiments, the first GBM alloy comprises at least neodymium, In another embodiment, the metals include praseodymium, dysprosium, cobalt, copper, and iron. Zr is also present. In another embodiment, nickel and / or cobalt are present in said first GBM alloy. and, if present, at least In another embodiment, iron and / or titanium may account for 36 atomic % of the first and, if present, together constitute at least one of the total composition of the first GBM alloy. It can occupy at most 2 atomic percent.

[0091] In some embodiments, the first GBM alloy is substantially composed of (Nd0.01-0.18 Pr 0.01-0.18 D y 0.3-0.5 Tb 0.3-0.5 ) aa (Co 0.85-0.95 Cu 0.04-0.15 Fe 0.01-0.08 ) bb (Zr 0.00-1.00 ) cc ; (In the formula: aa is a value within the range of 42 atomic % to 75 atomic %; bb is a value in the range of 6 atomic % to 60 atomic %; and cc is a value in the range of 0.01 atomic % to 18 atomic %; However, the total amount of Nd+Pr is more than 12 atomic %; However, the total amount of Nd+Pr+Dy+Tb is 95, 98, 99, 99.5, 99.8, or 99.9 atomic %. at least one of up to about 99.9 or 100 atomic %; However, the total amount of Co+Cu+Fe is greater than 95, 98, 99, 99.5, 99.8, or 99.9 atomic % and does not exceed about 99 0.9 or up to 100 atomic %; and However, aa+bb+cc is greater than 0.995 and up to about 0.999 or 1. In some embodiments, these compositions are represented by the formula: The more general formula AC is specified in the book b R x Co y Cu d M z is a subset of the formula Incorporate specific features.

[0092] In this formula, Nd and Pr are used in context (i.e., (Nd 0.01-0.18 Pr 0.01-0.18 Dy 0.3- 0.5 Tb 0.3-0.5 ) aa ), are independently described as being present in the range of 1 to 18 atomic %. In other embodiments, these independent ranges are 1-2 atomic %, 2-3 atomic %, 3-4 atomic % , 4~5 atomic %, 5~6 atomic %, 6~7 atomic %, 7~8 atomic %, 8~9 atomic %, 9~10 atomic %, 10~1 1 atomic %, 11-12 atomic %, 12-13 atomic %, 13-14 atomic %, 14-15 atomic %, 15-16 atomic %, 1 6 to 17 atomic %, 17 to 18 atomic %, or any combination of two or more of these ranges, e.g. For example, it can be further specified as 4 to 18 atomic %.

[0093] In this formula, Dy and Tb are used in context (i.e., Nd 0.01-0.18 Pr 0.01-0.18 Dy 0.3- 0.5 Tb 0.3-0.5 ) aa ), are independently described as being present in the range of 30 to 50 atomic %. In other embodiments, these independent ranges are 30-32 atomic %, 32-34 atomic %, 34-36 atomic %, atomic%, 36-38 atomic%, 38-40 atomic%, 40-42 atomic%, 42-44 atomic%, 44-46 atomic%, 46 48 atomic %, 48 to 50 atomic %, or any combination of two or more of these ranges, for example For example, it can be further specified as 36 to 42 atomic %.

[0094] In this formula, Co is used in the context (i.e., (Co 0.85-0.95 Cu 0.04-0.15 Fe 0.01-0.08 ) bb ), independently present in the range of 85 to 95 atomic %. In this case, these independent ranges are 85 to 85.5 atomic %, 85.5 to 86 atomic %, and 86 to 86.5 atomic %. , 86.5~87 atomic %, 87~87.5 atomic %, 87.5~88 atomic %, 88~88.5 atomic %, 88.5~89 atomic % , 89~89.5 atomic %, 89.5~90 atomic %, 90~90.5 atomic %, 90.5~91 atomic %, 91~91.5 atomic % , 91.5~92 at%, 92~92.5 at%, 92.5~93 at%, 93~94 at%, 94~95 at%, or may be any combination of two or more of these ranges, for example, 85 to 93 atomic %. It can be defined.

[0095] In this formula, Cu is used in context (i.e., (Co 0.85-0.95 Cu 0.04-0.15 Fe 0.01-0.08 ) bb ) are independently described as being present in the range of 4 to 15 atomic %. These independent ranges are 4-4.5 atomic %, 4.5-5 atomic %, 5-5.5 atomic %, 5.5-6 atomic % and %, 6-6.5 atomic %, 6.5-7 atomic %, 7-7.5 atomic %, 7.5-8 atomic %, 8-8.5 atomic %, 8.5 ~9 atomic%, 9~9.5 atomic%, 9.5~10 atomic%, 10~10.5 atomic%, 10.5~11 atomic%, 11~11.5 atomic%, 11.5-12 atomic%, 12-12.5 atomic%, 12.5-13 atomic%, 13-13.5 atomic%, 13.5-14 atomic %, 14 to 12.5 atomic %, 14.5 to 15 atomic %, or any two or more of these ranges The combination may be further specified as, for example, 85 to 93 atomic %.

[0096] In this formula, Fe is used in context (i.e., (Co 0.85-0.95 Cu 0.04-0.15 Fe 0.01-0.08 ) bb ), independently present in the range of 1 to 8 atomic percent. In this case, these independent ranges are 1-1.5 atomic %, 1.5-2 atomic %, 2-2.5 atomic %, 2.5-3 atomic %, and atomic %, 3-3.5 atomic %, 3.5-4 atomic %, 4-4.5 atomic %, 4.5-5 atomic %, 5-5.5 atomic %, 5. 5 to 6 atomic %, 6 to 6.5 atomic %, 6.5 to 7 atomic %, 7 to 7.5 atomic %, 7.5 to 8 atomic %, or any of these It may be further defined as any combination of two or more within the range, for example, 85 to 93 atomic percent. do.

[0097] In this formula, Zr is used in context (i.e., Zr 0.00-1.00 ) cc Independently 0 to 100 elements In another embodiment, these independent The ranges are 0-5 atomic %, 5-10 atomic %, 10-15 atomic %, 15-20 atomic %, 20-25 atomic %, 25 ~3 atomic %, 30~35 atomic %, 35~40 atomic %, 40~45 atomic %, 45~50 atomic %, 90~55 atomic % , 55-60 atomic %, 60-65 atomic %, 65-70 atomic %, 70-75 atomic %, 75-80 atomic %, 80-85 atomic %, 85-90 atomic %, 90-95 atomic %, 95-100 atomic %, or two or more of these ranges It may be further specified as any combination of the above, for example, 85 to 93 atomic %.

[0098] Such compositions include (Nd 0.16 Pr 0.06 Dy 0.39 Tb 0.39 ) aa (Co 0.85 Cu 0.12 Fe 0.03 ) bb (Zr 1.00 ) cc This can be more specifically described by the stoichiometric formula: may also independently be ±0.01, ±0.02, ±0.04, ±0.06 ±0.08, or ±0.1.

[0099] In independent embodiments, aa is 42 to 44 atom %, 44 to 46 atom %, 46 to 48 atom %, 48 atom % or atomic percent to 50 atomic percent, 50 to 52 atomic percent, 52 to 54 atomic percent, 54 to 56 atomic percent, 56 to 58 atomic percent, 58 to 60 atomic percent %, 60-62 atomic%, 62-64 atomic%, 64-68 atomic%, 68-70 atomic%, 70-72 atomic%, 72- 75 atomic % or any combination of two or more of these ranges, for example, 52 to 56 atomic % The value is in the range.

[0100] In another embodiment, bb is 6 to 8 atomic %, 8 to 10 atomic %, 10 to 12 atomic %, 12 to 14 atomic %. %, 14-16 atomic %, 16-18 atomic %, 18-20 atomic %, 20-22 atomic %, 22-24 atomic %, 24-26 atomic%, 26-28 atomic%, 28-30 atomic%, 30-32 atomic%, 32-34 atomic%, 34-16 atomic%, 36 ~38 atomic %, 38~40 atomic %, 40~42 atomic %, 42~44 atomic %, 44~46 atomic %, 46~48 atomic % , 48~50 atomic %, 50~52 atomic %, 52~54 atomic %, 54~56 atomic %, 56~58 atomic %, 58~60 atomic %, or any combination of two or more of these ranges, for example, in the range of 42 to 46 atomic %. In another embodiment, the range is defined by integer values ​​within these ranges. Examples of such items include:

[0101] In yet another embodiment, cc is 0.01 to 0.02 atomic %, 0.02 to 0.03 atomic %, 0.03 to 0. 0.04 atomic %, 0.04 to 0.05 atomic %, 0.05 to 0.06 atomic %, 0.06 to 0.07 atomic %, 0.07 to 0.8 atomic % , 0.08-0.09 atomic %, 0.09-0.1 atomic %, 0.1-0.2 atomic %, 0.2-0.3 atomic %, 0.3-0.4 atomic % atom%, 0.4-0.5 atom%, 0.5-0.6 atom%, 0.6-0.7 atom%, 0.7-0.8 atom%, 0.8-0.9 atom atom%, 0.9-1 atom%, 1-2 atom%, 2-3 atom%, 3-4 atom%, 4-5 atom%, 5-6 atom%, 6-7 atomic %, 7-8 atomic %, 8-9 atomic %, 9-10 atomic %, 11-12 atomic %, 12-13 atomic %, 13 up to 14 atomic %, 14 to 15 atomic %, 15 to 16 atomic %, 16 to 17 atomic %, 17 to 18 atomic %, or any of these Any combination of two or more within the range, for example, a value within the range of 0.8 to 1.6 atomic %. In another embodiment, the ranges are defined by integer values ​​or tenths of integer values ​​within these ranges. Examples include:

[0102] In one specific embodiment, the alloy comprises Nd 0.9 Pr 0.3 Dy 0.21 Tb 0.22 Co 0.38 Cu 0.05 Fe 0.01 Zr 0.01 (or alternatively: (Nd 0.16 Pr 0.06 Dy 0.39 Tb 0.39 ) 54.4 (Co 0.85 Cu 0.12 Fe 0.03 ) 44.9 (Zr 1.00 ) 0.62 Assuming that it corresponds to (can be described as follows): Nd 8.7±0.4 atomic %; Pr 3.3±0.4 atomic %; Dy 21.2±0.4 atomic %; Tb 21. 2±0.5 atomic %; Co 38.2±0.5 atomic %; Cu 5.4±0.4 atomic %; Fe 1.3±0.3 atomic %; Zr 0.6± In a related embodiment, each element in the composition is represented by a stoichiometry of 0.5 atomic percent. The raw variations are independently ±4.0, 3.0, 2.0, 1.8, 1.6, 1.4, 1.2, 1.0, 0.9, 0.8, 0.7, 0 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 atomic percent.

[0103] Next, again, a second core alloy is formed, substantially of the formula GFe 14 Think of it as being represented by B The material may be derived from virgin or recycled materials, in either case at will. and optionally doped with one or more dopants. Again, these descriptions are intended to be construed as meaning: Whether relating to the composition itself or to its use in one or more methods, This applies to core alloys.

[0104] By virtue of their chemical properties, the second core alloys can be magnetic, paramagnetic, ferromagnetic, or antiferromagnetic. They are paramagnetic, superparamagnetic, or can be made so under appropriate conditions. can exhibit such properties in the final sintered body.

[0105] As stated above, G is defined to include rare earth elements, where G is defined herein as R The term "rare earth element" is most broadly defined in terms of a rare earth element or combination of rare earth elements defined in terms of: In a preferred embodiment, G is Nd, Pr, La, Ce, Gd, Ho, Er, Yb, Dy, Tb, or any of the foregoing. In another preferred embodiment, G is defined in terms of a combination of P In yet another preferred embodiment, G is Nd with or without r. The term "substantially Nd" as used herein means that the rare earth element content is predominantly Nd. (e.g., greater than 95 atomic %, greater than 98 atomic %, or greater than 99 atomic %, but not doped with other rare earth elements) The nature of the rare earth element(s) in the second core alloy on a chemical or stoichiometric or ratio basis, or a combination thereof, the first GBM Note that this may be the same as or different from that in the alloy. The rare earth combinations in one GBM and the second core alloy are different.

[0106] The second core alloy is further optionally doped with one or more transition metal elements or main group elements. In some embodiments, these dopants include Dy, Gd, Tb, Al, Co, Cu, In still more specific embodiments, the composition comprises one or more of: Fe, Ga, Ti, or Zr. The second core alloy may further optionally comprise up to 6.5 atomic % Dy; up to 3 atomic % Gd; up to 6.5 atomic % Zr; at.% Tb; up to 1.5 at.% Al, up to 4 at.% Co, up to 0.5 at.% Cu, up to 0. 5 atomic % Fe, at most 0.3 atomic % Ga, at most 0.2 atomic % Ti, at most 0.1 atomic % Zr, or In an independent embodiment, the second core alloy is doped with a combination thereof. is 0-0.5 atomic %, 0.5-1 atomic %, 1-1.5 atomic %, 1.5-2 atomic %, 2-2.5 atomic %, 2.5-3 atomic %. atomic %, 3-3.5 atomic %, 3.5-4 atomic %, 4-4.5 atomic %, 4.5-5 atomic %, 5-5.5 atomic %, 5. 5 to 6 atomic %, 6 to 6.5 atomic %, or any combination of two or more of these ranges In an independent embodiment, the second core alloy may be doped with Dy in the range of 0 to 0. 5 atomic %, 0.5-1 atomic %, 1-1.5 atomic %, 1.5-2 atomic %, 2-2.5 atomic %, 2.5-3 atomic %, 3 ~3.5 atomic %, 3.5~4 atomic %, 4~4.5 atomic %, 4.5~5 atomic %, 5~5.5 atomic %, 5.5~6 atomic % %, 6 to 6.5 atomic % Tb, or any combination of two or more of these ranges. In an independent embodiment, the second core alloy contains 0 to 0.5 atomic percent of , 0.5 to 1 atomic %, 1 to 1.5 atomic %, 1.5 to 2 atomic %, 2 to 2.5 atomic %, 2.5 to 3 atomic %, or The compound may be doped with Gd within any combination of two or more of these ranges. In certain embodiments, the second core alloy may contain 0-0.5 atomic %, 0.5-1 atomic %, 1-1.5 atomic % or more of Al. %, or any combination of two or more of these ranges. In an independent embodiment, the second core alloy may contain 0 to 0.5 atomic %, 0.5 to 1 atomic % , 1-1.5 atomic %, 1.5-2 atomic %, 2-2.5 atomic %, 2.5-3 atomic %, 3-3.5 atomic %, 3.5-4 atomic % %, or any combination of two or more of these ranges. In an independent embodiment, the second core alloy may contain 0 to 0.05 atomic %, 0.05 to 0.1 atomic%, 0.1-0.15 atomic%, 0.15-0.2 atomic%, 0.2-0.25 atomic%, 0.25-0.3 atomic%, 0.3 0.35 atomic %, 0.35 to 0.4 atomic %, 0.4 to 0.45 atomic %, 0.45 to 0.5 atomic %, or within these ranges The doping may be performed with Cu in any combination of two or more of the above ranges. In some embodiments, the second core alloy may contain 0-0.05 atomic %, 0.05-0.1 atomic %, 0.1-0.15 atomic % or %, 0.15-0.2 atomic %, 0.2-0.25 atomic %, 0.25-0.3 atomic %, 0.3-0.35 atomic %, 0.35-0. 4 atomic %, 0.4 to 0.45 atomic %, 0.45 to 0.5 atomic %, or any two or more of the above ranges In an independent embodiment, the second The core alloys are 0-0.05 atomic %, 0.05-0.1 atomic %, 0.1-0.15 atomic %, 0.15-0.2 atomic %, 0. 2 to 0.25 atomic %, 0.25 to 0.3 atomic %, or any combination of two or more of these ranges In an independent embodiment, the second core alloy may be doped with Ga in the range , 0-0.01 atomic %, 0.01-0.02 atomic %, 0.02-0.03 atomic %, 0.03-0.04 atomic %, 0.04-0.0 5 atomic %, 0.05 to 0.06 atomic %, 0.06 to 0.07 atomic %, 0.07 to 0.08 atomic %, 0.04 to 0.09 atomic % , 0.09~0.1 atomic %, 0.1~0.11 atomic %, 0.11~0.12 atomic %, 0.12~0.13 atomic %, 0.13~0. 14 atomic %, 0.14-0.15 atomic %, 0.15-0.16 atomic %, 0.16-0.17 atomic %, 0.17-0.18 atomic % , 0.18 to 0.19 atomic %, 0.19 to 0.2 atomic %, or any combination of two or more of these ranges In an independent embodiment, the second core alloy may be doped with Ti within the range of Gold: 0-0.005 atomic %, 0.005-0.01 atomic %, 0.01-0.015 atomic %, 0.015-0.02 atomic %, 0 0.02 to 0.025 atomic %, 0.025 to 0.03 atomic %, 0.03 to 0.035 atomic %, 0.035 to 0.04 atomic %, 0.04 ~0.045 atomic %, 0.045~0.05 atomic %, 0.05~0.055 atomic %, 0.055~0.06 atomic %, 0.06~0. 0.065 atomic %, 0.065 to 0.07 atomic %, 0.07 to 0.075 atomic %, 0.075 to 0.08 atomic %, 0.08 to 0.085 atomic %, 0.085 to 0.09 atomic %, 0.09 to 0.095 atomic %, 0.095 to 0.01 atomic %, or within these ranges It may be doped with Zr in any combination of two or more of the above ranges.

[0107] Manufacturing of green compacts

[0108] The mixed alloy particles are (c) heated to a temperature of 1000° C. for 1 hour in an inert atmosphere. They are compressed together under a magnetic field of sufficient strength to align the magnetization in the direction of the magnetization. These particles are further processed by packing them together in a compact. The shape may be designed to facilitate the process. Mixtures of powder particles with different shapes can be obtained by mixing powder particles in a compact. This can help improve the packing efficiency of the gold powder. A solid body is provided containing an intimate mixture of alloy particles. The mixed alloy particles are then mixed into the final sintered body. The sintered body may be compressed into any desired shape suitable for its intended use. This may reflect the intended final shape or may require further processing to achieve the final shape of the sintered body. A cylindrical shape is typically preferred. In another embodiment, the mixed alloy particles are compressed in dry form; Suitable lubricants include, for example, fatty acid esters or amides or polyglycols. However, when the green compact is sintered, C, N, or O residues are left in the sintered compact. The level must be selected so that there is no or an acceptable level of residue. C, N, and / or O are typically individually less than 5000 ppm by weight, 2500 ppm, 1000 ppm, 1 It is less than 00 ppm or less than 10 ppm.

[0109] As used throughout this disclosure, the term "inert atmosphere" refers to an atmosphere free of oxygen, water, or other It refers to an atmosphere or environment that is substantially free of oxidizing agents. the absence of naturally added oxygen, water, or other oxidizing agents, and preferably the exclusion of these substances. Typically, dry nitrogen or air is used to remove the airborne particles. A argon atmosphere is suitable for this purpose.

[0110] During the formation of the green compact, the compaction is typically carried out under a compressive force in the range of about 800 to about 3000 kN. However, the method is not suitable for applications where the applied force is deemed desirable for the final process and product. It is not necessarily limited to these force levels, provided that the required density is met. In another embodiment, the force is applied in one or more applications, where each application is 800 ~1000kN, 1000~1500kN, 1500~2000kN, 2000~2500kN, 2500~3000kN, or any of these In some preferred embodiments, the compression includes applying a force within any combination of the above. is performed by applying a force in the range of about 1000 kN to about 2500 kN.

[0111] During the formation of the compact, the material may also be in the range of about 0.2T to about 2.5T or may contain magnetic particles. They are subjected to a magnetic field (160-2000 A / m) strong enough to align them in a common magnetization direction. In some embodiments, the magnetic field is 0.2 to 0.5 T, 0.5 to 1 T, 1 to 1.5 T, 1.5 to 2 T, 2 to 2.5 T, or Any combination of two or more of these ranges may be added in at least one range. do.

[0112] Sintering of green compacts

[0113] In some embodiments, the method further comprises (d) sufficiently sintering the green compact into a sintered body. and heating the powder compact to at least one temperature in the range of about 800°C to about 1500°C for a sufficient period of time. Further, the range for such sintering includes 800°C to 850°C, 850°C to 900°C, 900℃~950℃, 950℃~1000℃, 1000℃~1050℃, 1050℃~1100℃, 1100℃~1150℃, 115 0℃~1200℃, 1200℃~1250℃, 1250℃~1300℃, 1300℃~1350℃, 1350℃~1400℃, 140 0℃ to 1450℃, 1450℃ to 1500℃, or any two or more of these ranges The specific sintering conditions depend on the chemical properties and physical morphology of the particles in the compact (e.g. , chemical composition and particle size), in some embodiments: Some of these compositions are prepared at temperatures of about 1050 to about 1085°C for about 1 to 5 hours; typically In some embodiments, sintering may occur at about 1080° C. for 3.5 hours. The sintering process involves a combination of cyclic vacuum and inert gas (e.g., argon) pressures. It will be carried out under

[0114] Once the sintered body is formed, it is further (e) annealed. Heat treatment in a periodic vacuum and inert gas environment at a temperature in the range of about 450°C to about 600°C. It is also possible to understand

[0115] In another embodiment, the sintered body or body being sintered has (f) a thermal conductivity of, for example, about 400 kA / m to about 1200 kA / m. / m (0.5-1.5 T) to obtain the final remanence and It is magnetized by applying a magnetic field of sufficient strength to achieve coercivity. The magnetic field may be applied during sintering, after sintering, during annealing, after annealing, or at any time between these times. It may be applied between any two or more.

[0116] sintered magnets

[0117] Generally, the structure of the sintered body is composed of sintered core-shell grains held together by grain boundary compositions, Each of these core-shell grains may be described in terms of the R of the first GBM alloy. The second core alloy particles are formed by the diffusion of Cu, Co, and M elements into the matrix. a second core alloy surrounded by a plurality of shells, the shells being shells containing intermediate alloy compositions The grain boundary composition can thus be described in terms of the core containing the composition. The composition of the first GBM alloy minus any portion of elements that have migrated into the grains or intragranular regions.

[0118] Such compositions may each be "coated" with particles of the first GBM alloy. During sintering of the unique mixed alloy particles, which can be envisioned as containing a second core alloy, It may be seen as forming during the subsequent aging / annealing step of the sintered body. While not intending to be necessarily bound by the accuracy of any particular theory, it is believed that the lower melting point The GBM alloy distributes itself substantially homogeneously around and between the grains of the second core alloy particles. It can be assumed that, upon continued heating, the mobile and diffusible molecules of the first GBM alloy are distributed. The elements migrate into the matrix of the second alloy core particles. The grain boundaries act as a depot for the migration of elements of the first alloy into the second core alloy grain. Because the GBM alloy is made up of many elements, the individual atoms of the elements are separated into grains. The rate of diffusion of elements is a function of their specific chemical potential. The main G2Fe that results in the formation of a shell of elements 14 It exhibits a characteristic ability to move into phase B. Thus, the grain boundaries tend to reflect the original composition of the first GBM alloy, i.e., the overall composition is , defined in terms of the composition and ratio of the original components, and which are increased or depleted during processing. The arrangement of these components may be affected by the presence of SiO2 and nitrogen additives, but the arrangement of these components may be affected by the presence of nitrogen additives and nitrogen additives. The grain boundaries may change during sintering due to migration into the grains (and vice versa). The phrase "tends to reflect the original composition of the GBM alloy" refers to the compositional changes occurring at the grain boundaries. It is intended to imply that this can be attributed to the migration of atoms into the grains.

[0119] As a result, in some embodiments, some of the transition metal elements are present in the shell and Alternatively, some rare earth elements may be present in the shell but not in the grain core. Grain boundaries (especially triple junction boundaries) may be present in the grains or grain boundaries. In these embodiments, The concentrations of the migrating or diffusing elements are higher in the grain boundary composition than in the grain itself. The temperature difference provides a chemical gradient that drives the migration of elements into the grain. In an embodiment, both the sintered grains and the grain boundary alloy contain cobalt and copper, so that the grain boundary is enriched in these elements compared to their presence in the sintered particles. In some embodiments, the grain boundary alloy has at least 100% of the total composition of the alloy as measured by EDS. Also containing cobalt and copper in a combined amount of 20 wt.%, each of which accounts for 10 wt.% of the total alloy composition. It contains at least three rare earth elements and one transition element, not exceeding 1.

[0120] Consistent with the diffusion / migration theory described herein, the size of the grain core is affected by the processing, sintering, and This may depend on the thermal history of the particles or sintered body, including sintering and subsequent annealing steps. If the shell is formed from the inward migration or diffusion of elements of the first GBM alloy, then the original first Only the central portion of the core alloy particle of 2 retains its original compositional properties, and the resulting One would expect that the size of the core that forms would depend on the thermal history of the particle. The core of the present invention is characterized by a longer heat treatment and a more uniform grain boundary composition. At higher temperatures, more material is expected to move inwards, resulting in a smaller size. This improvement in magnetic performance (see examples) is due to the smaller size of the second core alloy. Consistent with the formation of a core. For example, Nd2Fe 14 Smaller grains (domains) of B (e.g., 300 nm) However, larger grains (e.g., >5 microns) exhibit higher remanence and better overall It is known that these materials exhibit synthetic magnetic properties (such as those demonstrated here). The sintered body containing these smaller grains is allowed to form the larger grains during sintering. The method was to provide these smaller G2Fe 14 B particles can be controlled means for achieving this, wherein the grains are separated by defined shells, It seems to provide a step.

[0121] Therefore, it is possible to control the size of the core in these GBE magnets and Embodiments defined by size are within the scope of this disclosure. The sintered body has a core of the second core alloy having dimensions in the range of about 0.3 to about 3.9 microns. In another embodiment, the grain core has a diameter of 0.3 to 0.4 microns, 0.4 to 0.5 microns. , 0.5-0.6 microns, 0.7-0.8 microns, 0.8-0.9 microns, 0.9-1 micron, 1-1.1 Micron, 1.1-1.2 micron, 1.2-1.3 micron, 1.3-1.4 micron, 0.4-0.5 micron , 1.5~1.6 microns, 1.7~0.8 microns, 1.8~1.9 microns, 1.9~2 microns, 2~2.1 microns Kron, 2.1-2.2 microns, 2.2-2.3 microns, 2.3-2.4 microns, 2.4-2.5 microns, 2.5-2.6 microns, 2.6-2.7 microns, 2.7-2.8 microns, 2.8-2.9 microns, 2.9-3 microns Kron, 3-3.1 microns, 3.1-3.2 microns, 3.2-3.3 microns, 3.3-3.4 microns, 3. 4~3.5 microns, 3.5~3.6 microns, 3.7~3.7, 3.7~3.8 microns, 3.8~3.9 microns, or any combination of two or more of these ranges, for example, about 0.3 to about 2.3 microns. Those skilled in the art will appreciate that the processing methods described herein may be used to fabricate a substrate having at least one dimension within the range. The core size of each composition can be adjusted by adjusting the process temperature, especially the final sintering temperature. It would be possible to determine the optimum range for any material by determining the optimum range for a given core alloy composition. The thickness of the shell is less important than the size of the core. However, in some embodiments, the cumulative thickness of the shell is in the range of about 1 to 3 microns. In some embodiments, the cumulative thickness of the shell is within about 0.5 to 1, 1 to 1.5, 1. 5~2.2~2.5, 2.5~3, 3~3.5, 3.5~4, 4~4.5, 4.5~5, or within these ranges Within the range defined by any two or more of

[0122] If the grains are spherical or quasi-spherical, their core dimensions are the diameter of the spherical or quasi-spherical core. For grains of other shapes, the optimum size may reflect the size of at least one axial dimension. It is also possible to describe the core in terms of its proportion to the shell(s). In some embodiments, it may be advantageous to have a ratio of core size to shell thickness. The ratio is in the range of about 1:10 to about 4:1. In another embodiment, the shell thickness of the core dimension The relative ratio to the amount of water is about 1:10 to about 1:8, 1.8 to about 1:1.6, about 1:6 to about 1:4, about 1:4 to about 1:2, Within the range of about 1:2 to about 1:1, about 1:1 to about 2:1, about 2:1 to about 3:1, or about 3:1 to about 4:1, or within these ranges The range is defined by two or more of the following:

[0123] The formation of the shell structure and the diffusion of heavy rare earths and other elements into each magnetic grain are important factors for the development of magnetic materials using this material. This allows them to be present throughout any magnet made with , with no limitations on thickness or geometry, using a minimum of Dy, Tb, or other rare earth elements. High coercivity magnets can be made (see, for example, Example 3, Table 13). The sintered body is chemically homogeneous or substantially homogeneous (as practically possible by solid-state mixing). As a result of sintering of mixed alloy particles, any (sintered core) so produced The composition of the sintered body (cell grains and grain boundaries) is substantially constant throughout the body (e.g., magnetic (Their physical properties may change by less than 10%, 5%, 4%, 3%, 2%, or 1%). "Substantially constant" means that the additive is not otherwise present on one or more surfaces of the previously sintered body. The substantial absence of compositional gradients across the sintered body that would result from the addition of The variance of these gradients is described elsewhere in this specification. The size and shape limitations of the homogeneous magnets so produced compared to magnets produced in stages That is, the substantial uniformity of any magnetic material so produced is no longer limited to grain boundaries. The boundary additive is not limited to diffusion into the pre-sintered body.

[0124] While not intending to be bound by the accuracy of any particular theory of action, Well-defined small G2Fe enclosed 14 The presence of the B core results in improved localized crystalline magnetization. If so, the GBM alloys are likely to be the cause of the anisotropy. Each of the elements provided is believed to provide a particular attribute to the final product. For example, the addition of transition metals (Cu, Co, Zr, Fe additives) improves the temperature resistance to magnetization reversal. The introduction of Cu at the levels claimed for the GBM additive appears to increase the triple potential. Kett joint (grain boundary phase) and G2Fe 14 B / Nd2Fe 14 Within the boundaries between B matrix grains, (i) GFe 14 B / Nd2Fe 14 B Increase in surface energy between matrix grains and grain boundaries, and (ii) N of Dy and Tb d2Fe 14B) provide one or both of the formation of thin layers that inhibit diffusion into the matrix grains. It is believed that the addition of Cu at levels sufficient to induce the formation of copper-rich aggregates. Not only does it increase corrosion resistance by forming various copper-rare earth metal oxides, but it also This is believed to help resist embrittlement of the final core-shell sintered NdFeB product.

[0125] While not intending to be bound by the accuracy of any particular theory of action, GBM addition Introducing Co at the claimed levels for the agent results in a core-multishell structure. In addition, core-shell sintered NdFeB (G2Fe 14 B phase) has increased corrosion resistance in the grain boundary phase Thus, the formation of rare earth-cobalt oxide phase(s) may help inhibit corrosivity. It is believed to be connected.

[0126] While not intending to be bound by the accuracy of any particular theory of action, GBM alloys The presence of Zr in the first or second alloy is due to the presence of Zr in the second alloy. It is believed that this results in the association of any iron present in the grains with the iron. In some cases, the coalesced Zr-Fe alloy is useful in preventing the propagation of inversion domains during demagnetization. The presence of Zr may also alter the electron concentration within any such associated Fe-Zn structure. By this, the grain boundaries and the matrix G2Fe 14 Ferromagnetic coupling between the B phase and The introduction of Zr on the grain boundaries is believed to increase the resistance in the final core-shell sintered NdFeB product. It may also help to increase the resistance.

[0127] While not intending to be bound by the accuracy of any particular theory of action, GBM addition The addition of various rare earth elements (Nd, Pr, Dy, Tb) by the additive also alters the magnetocrystalline anisotropy around the core. This is believed to result in the formation of rare earth-rich shell(s) that allow for the strengthening of Each element in the GBM additive is expected to have a different diffusivity into the core material. The overall presence of these materials, Nd, Pr, Dy, Tb, Cu, Co, Zr, and Fe, in amounts that are expected to be present in the grains Kinetic and thermodynamic properties to regulate the diffusion of these and other species into the bulk Seems to offer the best balance of qualities.

[0128] Furthermore, their relative strength will depend on the rate of diffusion of the material into the core under processing conditions. It is expected that individual bands (shells) for each migrating species will be observed. For example, a second G2Fe alloy containing Dy, Tb, Cu, and Co (from the first GBM alloy) 14 B core alloy material The intensity of diffusion into the material depends on the migration kinetics of these individual (or aggregate) molecules. This results in bands of each of these materials within the final grain structure within the outer shell of the alumina. If multiple heat treatments are applied, the shells of these individual elements are formed by the subsequent heat treatments. Depending on their local environment at the time, they may broaden or separate. The material has a small amount of lattice defects at the grain boundaries, which act as reservoirs for their subsequent migration. If we assume that these materials are at least initially present, then the G2Fe 14 B core expansion The diffusion is calculated as (C0*exp(-x / L)*sin(x / l+c)) where C0 is the initial concentration of each element at the grain boundary and L is where l is the decay length and l is the diffusion wavelength under the processing conditions. This can be modelled as a periodic trend.

[0129] These GBE magnets are much more durable than other methods of achieving similar properties. It can be manufactured using much lower levels of rare earth elements such as Dy, Tb, and Er. Not only for this reason, but even at these reduced Dy levels, the resulting magnet are attractive because they exhibit similar or superior properties (see Tables 11-13). Compositions exhibiting such improved properties are also within the scope of this disclosure. Thus, such magnets have increased coercivity (up to 90%) with minimal loss of remanence. Such materials also offer enhanced corrosion resistance and resistance to demagnetization. It shows greater alpha and beta factors, which indicates higher resistance. The GBE magnets described herein are reversible, particularly when they are made of Dy, Tb, Co, Cu, Fe, or Zr. provides a significant improvement in the typical coefficients alpha (which describes remanence) and beta (which describes coercivity) GBE magnets exhibiting such improved properties are also within the scope of the present invention. This embodiment exhibits excellent thermal conductivity over a temperature range of 80°C to 200°C when tested under the conditions described in Example 3. Heavy rare earth elements independently exhibiting |α| values ​​in the range of 0.02 to 0.14 or |β| values ​​in the range of 0.45 to 0.7. element (i.e., Dy, Tb, Ho, Er, Tm, Yb, or Lu, but especially Dy) in an amount of 0.2 to 0 .3wt%, 0.3~0.4wt%, 0.4~0.5wt%, 0.5~0.6wt%, 0.6~0.7wt%, 0.7~0 .8% by weight, 0.8~0.9% by weight, 0.9~1.0% by weight, 1.0~1.1% by weight, 1.1~1.2% by weight, 1.2~1 .3% by weight, 1.3~1.4% by weight, 1.4~1.5% by weight, 1.5~1.6% by weight, 1.6~1.7% by weight, 1.7~1 0.8% by weight, 1.8-1.9% by weight, 1.9-2% by weight, or any two or more of these ranges combinations, for example, at levels in the range of 0.1 to 1.3 wt. % or 0.8 to 1.3 wt. %. Doped or undoped G2Fe 14 B (dopant levels are described elsewhere herein) Nominally Nd2Fe 14 The GBE composition includes a core comprising:

[0130] At the risk of repeating myself, I would like to mention, in particular, Nd2Fe 14 Specifically, as having a B core For the indicated composition, the specific properties that characterize the sintered body include: Can be: Grains in the range of about 3 microns to about 5 microns; characterized in that the grains have a core and multiple the grain having a number of shell layers; NdFe in these grains has a size of 0.3 to about 2.3 to 2.9 microns 14 B-core; Multiple individual transition metal (Co, Cu, and M) elements form peripheries extending from the grain boundaries to the core of each grain. A matrix of a second core alloy (in this case NdFe) is placed within the final shell. 14 B) together Multiple shells distributed in; The non-core GBM alloy material is enriched, reflecting higher concentrations of transition metal (Co, Cu, and M) elements. (wherein M is at least one transition metal element excluding Cu and Co) · Elements in the grain shell layer that reflect elements in the GBM alloy; A comparative composition (having the same grain size and overall elemental composition, but the grains of the comparative composition The composition exhibits the following properties compared to the present invention (without a concentric shell): Properties may also be characteristic.

[0131] Again, for the sake of completeness, it is understood that the present disclosure includes alloys, alloy and mixed alloy particles, alloy particles, Agglomerates, green compacts, sintered bodies, and their associated grains and grain boundaries, and the structure of these articles It should be noted that this includes descriptions of processes. Any description that can be attributed to a process can also be attributed to an article. and vice versa.

[0132] In addition to the sintered magnetic compositions themselves, additional embodiments include devices incorporating these magnets. Such devices are intended for use at temperatures within the range of 80°C to 200°C. Such devices include computer or tablet hard disks. head actuators, erase heads, magnetic resonance imaging (MRI) equipment, magnetic locks, magnetic Air fasteners, speakers, headphones or earphones, mobile phones and other household appliances Products (e.g., iPods, electronic watches, earphones, DVD and Blu-ray players, CDs and record players, microphones, household appliances), magnetic bearings and magnetic cups rings, NMR spectrometers, linear and A / C motors, electric motors (e.g., cordless Stools, servo motors, compression motors, synchronous motors, spindle motors, and Stepping motors, electric steering and power steering, hybrid vehicles and and electric vehicle drive motors), and generators (wind turbines, (including ).

[0133] system

[0134] In addition to the structure, preparation, and methods of use of the inventive materials, this disclosure also provides methods for preparing these materials. Again, methods for making these core-shell materials are provided. Many of the statements made in this document are applicable to the description of the system, and to the extent appropriate, these statements are incorporated herein by reference. is incorporated here.

[0135] For example, in homogenizing the first GBM alloy particles and the second core alloy particles: (a) an adiabatic rotary reactor, the reactor having an inlet port and an outlet port, each Ports are adapted to add and remove particles from the rotary reactor, respectively. Each inlet port and outlet port is optionally fitted with a particle sieve. Thermal rotary reactor; (b) a vacuum source capable of providing a vacuum to the adiabatic rotary reactor; (c) a heater capable of heating the rotary reactor during use; and optionally; (d) a sampling portal that allows for the collection of samples while the device is in operation; It is convenient to use a device comprising:

[0136] While each of these particular elements is individually known, the combined device is similarly not. There is no.

[0137] Furthermore, systems comprising such devices may be used to carry out the methods described herein. wherein the system may be useful for: (a) subjecting the solid magnetic material to a pressure of 1 to 10 bar (or, in some embodiments, less than Rotary hydrogen reactors capable of processing hydrogen at pressures in the range of high (e.g., up to 150 bar) Apparatus; (b) A rotary degasser that is evacuated and heated to produce thermal cracking of hydrogen-containing magnetic materials. Member; (c) Jet mill equipment; (d) a compression device capable of applying a force in the range of about 800 to about 3000 kN to a group of particles; The compression device has a magnetic field source attached thereto, and the magnetic field source providing a magnetic field in the range of about 0.2 T to about 2.5 T while applying the force to the population of particles. the compression device; and (e) a sintering chamber, the chamber being heated to temperatures ranging from ambient to about 400°C, and further to about Selective vacuum and inert atmospheres are provided within the chamber while providing an internal temperature in the range of up to 1200°C. the sintering chamber configured to provide an ambient environment; Further, the present invention includes one or more of the following:

[0138] In another embodiment, such a system comprises two or three of these aspects (a)-(e). Contains one, four, or five.

[0139] The following list of embodiments does not replace or supersede the previous description. Rather, they are intended to be complementary. Thus, these embodiments are not intended to be limiting in the context of the general description. It should be read in

[0140] (Embodiment 1) 1. A method for producing a sintered magnetic body having improved coercivity and remanence, comprising: (a) combining a first population of particles of a first GBM alloy with a second population of particles of a second core alloy; The weight ratio of the first and second populations is in the range of about 0.1:99.9 to about 16.5:83.5, and the mixture is homogenized. forming an alloy preform; (i) the first GBM alloy has a composition substantially of the formula: AC b R x Co y Cu d M z (In the formula, (A) AC contains Nd and Pr in an atomic ratio within the range of 0:100 to 100:0, and b is about 5 atomic % a value in the range of ∼65 atomic %; (B) R is one or more rare earth elements, and b is in the range of about 5 atomic % to about 75 atomic %. is the value of; (C) Co is cobalt and Cu is copper; (D) y is a value within the range of about 20 atomic % to about 60 atomic %; (E) d is a value in the range of about 0.01 atomic % to about 12 atomic %; (F) M is at least one transition metal element other than Cu and Co, and z is about 0.01 atom. % to about 18 atomic %; and (G) The sum of b+x+y+d+z is 95, 96, 97, 98, 99, 99.5, 99.8, or 99.9 atomic % more than one, up to about 99.9 or 100 atomic % It is expressed as (ii) the second core alloy is substantially GFe 14 B (wherein G is a rare earth element) and the second core alloy contains one or more transition or main group elements (virgin or recycled). are optionally doped with any substance (including those brought about by the use of a dye); said homogenizing; (b) heating the composite alloy preform to a temperature above the solidus temperature of the first alloy but below the solidus temperature of the second core alloy; Heating to a temperature below the melting point of gold to form a population of discrete mixed alloy particles thing The method comprising:

[0141] (Embodiment 2) 1. A method for producing a sintered magnetic body having improved coercivity and remanence, comprising: (a) A first population of particles of a first grain boundary modified (GBM) alloy is combined with a second population of particles of a second core alloy. The weight ratio of the first and second populations of particles is homogenized within a range of about 0.1:99.9 to about 16.5:83.5. forming a composite alloy preform; The second core alloy is substantially of the formula GFe 14 B (wherein G is a rare earth element) and optionally, the second core alloy is doped with one or more transition metal elements or main group elements. the law of nature; The first population of particles of the first GBM alloy has an average particle size in the range of about 1 micron to about 4 microns. Within the perimeter; The second population of particles of the second core alloy has an average particle size of about 2 microns to about 5 microns. within the range) said homogenizing; and (b) heating the composite alloy preform to a temperature above the solidus temperature of the first alloy but below the solidus temperature of the second core alloy; Heating to a temperature below the melting point of gold to form a population of discrete mixed alloy particles thing The method comprising:

[0142] (Embodiment 3) the first GBM alloy having a structure substantially of the formula Nd j Dy k Co m Cu n Fe p (In the formula, j is 1-2, 2-3, 3-4, 4-5, 5-6, 6-7, 7-8, 8-9, 9-10, 10 for all compositions ~11, 11~12, 12~13, 13~14, 14~15, 15~16, 16~17, 17~18, 18~19, 19~20 atoms %, or a range inclusive of two or more of these ranges; k is 1-5, 5-10, 10-15, 15-20, 20-25, 25-30, 30-35, 35- 40, 40-45, 45-50, 50-55, 55-60 20 atomic % range, or two of these ranges the atomic percent in the range inclusive of one or more; m is 1-5, 5-10, 10-15, 15-20, 20-25, 25-30, 30-35, 35- 40, 40 to 45, 45 to 50, 50 to 55, 55 to 60 atomic %, or two or more of these ranges in atomic percent within the inclusive range; n is 0.1-0.5, 0.5-1, 1-1.5, 1.5-2, 2-2.5, 2.5-3, 3-3.5 for all compositions , 3.5~4, 4~4.5, 4.5~5, 5~5.5, 5.5~6, 6~6.5, 6.5~7, 7~7.5, 7.5~8, 8.5~9 , 9 to 9.5, 9.5 to 10, 10 to 12, 12 to 14, 14 to 16, 16 to 18, 18 to 20 atomic %, or the atomic percentage being within a range inclusive of two or more of the ranges; p is 1-2, 2-3, 3-4, 4-5, 5-6, 6-7, 7-8, 8-9, 9-10, 10 for all compositions ~11, 11~12, 12~13, 13~14, 14~15, 15~16, 16~17, 17~18, 18~19, 19~20 atoms %, or a range inclusive of two or more of these ranges; or t j, k, m, n, and p are independently variable within their stated ranges, provided that j+k+m The sum of +n+p is greater than 95, 96, 97, 98, 99, 99.5, 99.8, or 99.9 atomic % to about 99.9 atomic % or up to 100 atomic % The method of embodiment 2, wherein

[0143] (Embodiment 4) Prior to the homogenizing step (a), either the first GBM or the second core alloy, or The coarse grains of both the first GBM and the second core alloy are subjected to hydrogen treatment in the presence of hydrogen. absorption of the hydrogen into either the second core alloy or both the first GBM and the second core alloy. 3. The method of claim 1 or 2, wherein the treatment is carried out under conditions and for a time that allows

[0144] (Embodiment 5)

[0023] Any of embodiments 1 to 3, wherein the homogenizing step (a) comprises multiple separate mixing steps. The method described in one.

[0145] (Embodiment 6) The homogenizing step (a) comprises a plurality of separate mixing steps, at least one of which At least one of the particle populations increases the average surface area of ​​at least one, preferably both, of the particle populations. The method according to any one of embodiments 1 to 4, wherein

[0146] (Embodiment 7) % of the first GBM alloy; The method according to any one of embodiments 4 to 6 as applied to embodiment 1. Related independent embodiments In the embodiment, b is 5 to 10 atomic %, 10 to 15 atomic %, 15 to 20 atomic %, 20 to 25 atomic %, 25 to 30 atomic %, 30-35 atomic %, 35-40 atomic %, 40-45 atomic %, 45-50 atomic %, 50-55 atomic %, 55 to 60 atomic %, 60 to 65 atomic %, or any combination of two or more of these ranges That is it.

[0147] (Embodiment 8) The atomic ratio of Nd to Pr in AC is 100:0, 25:75, 50:50, 75:25, or 0:100. The method according to any one of embodiments 4 to 7 as applied to embodiment 1 or embodiment 1.

[0148] (Embodiment 9) R is Nd, Pr, La, Ce, Gd, Ho, Er, Yb, Dy, Tb, or a combination thereof, preferably is Dy and / or Tb, In an independent subembodiment, R is 1, 2, 3, 4, 5, 6, 7, or 8. different rare earth elements, preferably at least 3, 4, 5, 6, 7, or 8 different rare earth elements. It may contain elements.

[0149] (Embodiment 10) R comprises at least three different rare earth elements, totaling about 10 atoms of the first GBM alloy. % to about 60 atomic % of the total amount of the hydroxybenzoates of embodiment 1 or any of embodiments 4 to 9 applied to embodiment 1. In an independent embodiment, and independently of the number of R elements present, , x is 5-10 atomic %, 10-15 atomic %, 15-20 atomic %, 20-25 atomic %, 25-30 atomic %, 30- 35 atomic %, 35-40 atomic %, 40-45 atomic %, 45-50 atomic %, 50-55 atomic %, 55-60 atomic %, 60 to 65 atomic %, 65 to 70 atomic %, 70 to 75 atomic %, or any two or more of these ranges Any combination of these ranges is acceptable; exemplary, non-limiting combination ranges include 30 to 60 atomic % or 1 The content may be 0 to 60 atomic %.

[0150] (Embodiment 11) %。 Co is present in the first GBM alloy in the range of about 35 atomic % to 45 atomic %. The method according to any one of embodiments 4 to 10, which is applied to embodiment 1. In the formula, y is 20 to 25 atomic %, 25 to 30 atomic %, 30 to 35 atomic %, 35 to 40 atomic %, 40 to 45 atomic %. %, 45 to 50 atomic %, 50 to 55 atomic %, 55 to 60 atomic %, or two or more of these ranges Any combination of the above ranges is acceptable; exemplary, non-limiting combination ranges include 30 to 40 atoms % are listed.

[0151] (Embodiment 12)

[0023] In one embodiment or another, Cu is present in the first GBM alloy in the range of about 0.01 atomic % to 6 atomic %. The method according to any one of embodiments 4 to 11, which is applied to embodiment 1. In the formula, d is 0.01 to 0.05 atomic %, 0.05 to 0.1 atomic %, 0.1 to 0.15 atomic %, 0.15 to 0.2 atomic %. %, 0.2 to 0.25 atomic %, 0.25 to 0.5 atomic %, 0.5 to 1 atomic %, 1 to 1.5 atomic %, 1.5 to 2 atomic %, 2-2.5 atomic %, 2.5-3 atomic %, 3-3.5 atomic %, 3.5-4 atomic %, 4-4.5 atomic %, 4.5-5 atomic %, 5-5.5 atomic %, 5.5-6 atomic %, 6-7 atomic %, 7-8 atomic %, 8-9 atomic %, 9-10 atomic % , 10 to 11 atomic %, 11 to 12 atomic %, 12 to 13 atomic %, 13 to 14 atomic %, 14 to 15 atomic %, or The ranges are any combination of two or more of the ranges.

[0152] (Embodiment 13) M is Ag, Au, Co, Fe, Ga, Mo, Nb, Ni, Ti, V, W, Y, Zr, or a combination thereof. The method according to any one of embodiments 1 to 12 as applied to embodiment 1, In an independent embodiment, M is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, At least 11, 12, or 13 distinct transition metal elements, preferably at least 11, 12, or 13 distinct transition metal elements, again excluding Cu and Co. Each may contain 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 distinct transition metal elements.

[0153] (Embodiment 14) 10. The method of claim 1, wherein M is present in the first GBM alloy in the range of about 0.01 atomic % to 10 atomic %. The method according to any one of embodiments 4 to 13, as applied to embodiment 1. In an independent embodiment, In this case, z is 0.01 to 0.05 atomic %, 0.05 to 0.1 atomic %, 0.1 to 0.15 atomic %, or 0.15 to 0.2 atomic %. , 0.2~0.25 atomic %, 0.25~0.5 atomic %, 0.5~1 atomic %, 1~1.5 atomic %, 1.5~2 atomic %, 2 ~2.5 atomic %, 2.5~3 atomic %, 3~3.5 atomic %, 3.5~4 atomic %, 4~4.5 atomic %, 4.5~5 atomic % %, 5-5.5 atomic %, 5.5-6 atomic %, 6-7 atomic %, 7-8 atomic %, 8-9 atomic %, 9-10 atomic % , 10 to 11 atomic %, 11 to 12 atomic %, 12 to 14 atomic %, 14 to 16 atomic %, 16 to 18 atomic %, or The ranges are any combination of two or more of the ranges.

[0154] (Embodiment 15) Nickel and / or cobalt are present in the first GBM alloy and, as a whole, the first GBM alloy % of the total composition of the GBM alloy. The method according to any one of embodiments 4 to 14.

[0155] (Embodiment 16) Iron and / or titanium are present in the first GBM alloy, and the first GBM alloy as a whole % of the total composition of gold. The method according to any one of embodiments 4 to 15, as applicable.

[0156] (Embodiment 17) G is Nd, Pr, La, Ce, Gd, Ho, Er, Yb, Dy, Tb, or a combination thereof, preferably Preferably, the method according to any one of embodiments 1 to 16 is Nd with or without Pr. Law.

[0157] (Embodiment 18) The first GBM alloy comprises at least neodymium, praseodymium, dysprosium, cobalt, and copper. and iron. The method described.

[0158] (Embodiment 19) G is Nd and / or Pr, and the second core alloy optionally contains at least one transition The method of any one of embodiments 1 to 18, further doped with a metal or metal.

[0159] (Embodiment 20) G is Nd and / or Pr, and the second core alloy is Dy, Gd, Tb, Al, Co, Cu, Fe 19. Any of embodiments 1-19, further doped with one or more of: Ga, Ti, or Zr. The method described in one.

[0160] (Embodiment 21) G is Nd and / or Pr, and the second core alloy contains up to 6.5 atomic % Dy, up to 3 atomic % Gd, up to 6.5 atomic % Tb, up to 1.5 atomic % Al, up to 4 atomic % Co, up to 0.5 atomic % Cu, up to 0.3 atomic % Ga, up to 0.2 atomic % Ti, up to 0.1 atomic % Zr, or or a combination thereof. How to do it.

[0161] (Embodiment 22) The first population of particles of the first GBM alloy has an average particle size in the range of about 1 micron to about 4 microns. 22. The method of any one of embodiments 1 to 21, wherein

[0162] (Embodiment 23) the second population of particles of the second core alloy has an average particle size of about 2 microns to about 5 microns; 23. The method of any one of embodiments 1 to 22, wherein the

[0163] (Embodiment 24) The average particle size of said population of said individually separated mixed alloy particles is between about 2 microns and about 6 microns. 24. The method according to any one of embodiments 1 to 23, wherein the particle size is preferably in the range of 3 to 4 microns. Law.

[0164] (Embodiment 25) The heating in (b) results in the formation of a cluster of individually separated mixed alloy particles, each a core of said second core alloy, said particles having a size within the range of about 1 to about 5 microns; Any one of embodiments 1-24, comprising a shell whose composition is defined by the elements of the first alloy. The method described below.

[0165] (Embodiment 26) (c) aligning the population of mixed alloy particles in an inert atmosphere with the magnetic particles in a common direction of magnetization; The powders are then compressed together under a magnetic field of suitable strength to align them, forming a compact. 26. The method of any one of embodiments 1 to 25, comprising:

[0166] (Embodiment 27) The compressing force is in the range of about 800 to about 3000 kN, preferably about 1000 kN to about 2500 kN. 27. The method of embodiment 26, wherein the method is carried out under force.

[0167] (Embodiment 28) The magnetic field is in the range of about 0.2 T to about 2.5 T, or the magnetic particles are aligned in a common direction of magnetization. 28. The method of embodiment 26 or 27, wherein the method is sufficient to sequence the

[0168] (Embodiment 29) (d) sintering the green compact into a sintered body comprising sintered core-shell grains and a grain boundary composition. and heating the powder compact to at least one temperature in the range of about 800°C to about 1500°C for a sufficient period of time. 29. The method of any one of embodiments 26 to 28, further comprising:

[0169] (Embodiment 30) (e) in a vacuum and inert gas environment with a periodic temperature in the range of about 450°C to about 600°C. 30. The method of claim 29, further comprising heat treating (annealing) the sintered body. .

[0170] (Embodiment 31) (f) of sufficient strength to achieve the final remanence and coercivity as described herein; A magnetic field, for example, a magnetic field in the range of about 400 kA / m to about 1200 kA / m (0.5 to 1.5 T), is used to control the sintering temperature. 31. The method of embodiment 29 or 30, further comprising applying to the body or sintered body.

[0171] (Embodiment 32) the sintered particles of the second core alloy having a size within the range of about 0.3 to about 2.9 microns. 32. The method of any one of embodiments 29 to 31, comprising a core.

[0172] (Embodiment 33) The sintered core-shell particles comprise a quasi-concentric shell surrounding the core, the shell comprising: The composition is defined by a shell layer of Co, Cu, and M elements within the matrix of the core alloy of 2. 33. The method of any one of embodiments 29 to 32. In some embodiments, the core diameter The relative ratio of the thickness of the shell to the thickness of the shell is in the range of about 1:25 to about 4:1. The relative ratio of the core diameter to the shell thickness is in the range of about 1:10 to about 4:1.

[0173] (Embodiment 34) The grain boundary alloy is enriched in cobalt and copper relative to their presence in the sintered grains. 34. The method according to any one of embodiments 29 to 33, wherein

[0174] (Embodiment 35) The grain boundary alloy has a total of at least 20% by weight of the total composition of the alloy as measured by EDS. Cobalt and copper in amounts not exceeding 10% by weight of the total alloy composition, and at least 35. The method of any one of embodiments 29 to 34, comprising three rare earth elements and one transition element. .

[0175] (Embodiment 36) The overall chemical composition of the alloy or particles is determined by inductively coupled plasma (ICP) analysis. The method according to any one of embodiments 1 to 35,

[0176] (Embodiment 37) The overall chemical composition within the grain or grain boundary is determined by the energy distribution across the fracture or polished surface. 37. Any one of embodiments 1 to 36, characterized using energy dispersive X-ray spectroscopy (EDS) mapping. The method described in the first paragraph.

[0177] (Embodiment 38) A particle or particle cluster produced by the method according to any one of embodiments 1 to 25 or 36. In some aspects of this embodiment, the particle or population of particles is a method-related composition. Although defined in terms of their composition, they are not necessarily produced by these methods.

[0178] (Embodiment 39) A powder compact produced by the method according to any one of embodiments 26 to 28 or 36 to 37. In some embodiments, the green compact is defined in terms of a composition related to the method of manufacture. However, they are not necessarily produced by these methods.

[0179] (Embodiment 40) A sintered body produced by the method according to any one of embodiments 29 to 37. The solids are characterized by their chemical composition and distribution within the grains and grain boundaries, as well as by structures that do not have these characteristics. The present embodiment may be characterized by its overall structure, including enhanced performance compared to the conventional structure. In some embodiments, the green compact is defined in terms of composition related to the method of manufacture, but is not necessarily It is not necessarily produced by these methods.

[0180] (Embodiment 41) 32. A device comprising the sintered magnetized body of claim 31, comprising: a computer; or tablet hard disk head actuators, erase heads, nuclear magnetic resonance imaging Magnetic Resonance Imaging (MRI) equipment, magnetic locks, magnetic fasteners, speakers, headphones or earphones , mobile phones and other consumer electronics (e.g., iPods, electronic watches, earphones, DVDs and Blu-ray players, CD and record players, microphones, household appliances), Magnetic bearings and magnetic couplings, NMR spectrometers, electric motors (e.g., cordless motors, servo motors, compression motors, synchronous motors, spindle motors, and step motors Ping motors, electric steering and power steering, hybrid vehicles and electric wind turbines), and generators (such as those used in wind vehicle drive motors) In some aspects of this embodiment, the device is selected from the group consisting of Sintered magnetized bodies are defined in terms of their composition that is related to their method of manufacture, but not necessarily to this. It is not produced by these methods.

[0181] (Embodiment 42) Formula:AC b R x Co y Cu d M z (In the formula: (A) AC contains Nd and Pr in an atomic ratio within the range of 0:100 to 100:0, and b is about 5 atomic % to a value in the range of about 65 atomic percent; (B) R is one or more rare earth elements, and x is in the range of about 5 atomic % to about 75 atomic %. is a value; (C) Co is cobalt and Cu is copper; (D) y is a value within the range of about 20 atomic % to about 60 atomic %; (E) d is a value in the range of about 0.01 atomic % to about 12 atomic %; (F) M is at least one transition metal element other than Cu and Co, and z is about 0.01 to about %; and (G) b+x+y+d+z exceeds one or more of 95, 98, 99, 99.5, 99.8, or 99.9 atomic % (up to about 99.9 atomic % or 100 atomic % A composition comprising an alloy represented by the formula: In an independent aspect of this embodiment, the alloy has a thickness of 0.5 microns to about 5 microns, or 0.5-0.8 microns, 0.8-1 microns, 1-2 microns, 2-2.5 microns, 2. Any one or combination of subranges including 5 to 3 microns, 3 to 4 microns, or 4 to 5 microns or a combination of two or more of these ranges, for example, 1 micron to 4 microns. It exists as a population of particles having an average particle size within the range of 100 nm.

[0182] (Embodiment 43) the atomic ratio of Nd to Pr in AC is 100:0, 25:75, 50:50, 75:25, or 0:100; or The composition of embodiment 42, in any ratio therebetween.

[0183] (Embodiment 44) R is La, Ce, Gd, Ho, Er, Yb, Dy, Tb, or a combination of two or more of these elements. 44. The composition of embodiment 42 or 43. In an independent aspect of this embodiment, R is L a combination of two, three, four, five, or six of a, Ce, Gd, Ho, Er, Yb, Dy, or Tb.

[0184] (Embodiment 45) M is Ag, Au, Co, Fe, Ga, Mo, Nb, Ni, Ti, V, W, Y, Zr, or a combination thereof. The composition of any one of embodiments 42 to 44. In an independent aspect of this embodiment, M is 2, 3, or 4 of Ag, Au, Co, Fe, Ga, Mo, Nb, Ni, Ti, V, W, Y, or Zr. , 5, or 6 types of combination.

[0185] (Embodiment 46) The alloy is substantially (Nd 0.01-0.18 Pr 0.01-0.18 Dy 0.3-0.5 Tb 0.3-0.5 ) aa (Co 0.85-0.95 Cu 0.04-0.15 Fe 0.01-0.08 ) bb (Zr 0.0-1.00 ) cc ;(in the formula: aa is a value within the range of 42 atomic % to 75 atomic %; bb is a value in the range of 6 atomic % to 60 atomic %; and cc is a value in the range of 0.01 atomic % to 18 atomic %; However, the total amount of Nd+Pr is more than 12 atomic %; However, the total amount of Nd+Pr+Dy+Tb is one of 95, 98, 99, 99.5, 99.8, or 99.9 atomic %. more than one or more up to about 99.9 or 100 atomic %; However, the total amount of Co+Cu+Fe is one of 95, 98, 99, 99.5, 99.8, or 99.9 atomic %. or more up to about 99.9 or 100 atomic %; and However, the sum of aa + bb + cc is greater than 0.995 and is up to about 0.999 or 1. 46. ​​The composition according to any one of embodiments 42 to 45, represented by the formula:

[0186] (Embodiment 47) The alloy is (Nd 0.16 Pr 0.06 Dy 0.39 Tb 0.39 ) aa (Co 0.85 Cu 0.12 Fe 0.03 ) bb (Zr 0.62 ) cc Chemistry of The composition of any one of embodiments 42 to 46, described by a stoichiometric formula: Any individual variation within this range may be independently within ±0.01, ±0.02, ±0.04, ±0.06, ±0.08, or ±0.005. It can be .1.

[0187] (Embodiment 48) the first population of particles of the first GBM alloy has an average particle size of about 1 micron to about 4 microns; The composition of any one of embodiments 42 to 47, which is within the range

[0188] (Embodiment 49) The composition according to any one of embodiments 42 to 48, which is a form containing columnar and spherical crystallites. Finished product.

[0189] (Embodiment 50) 50. The composition of any one of embodiments 42 to 49, which is in amorphous form.

[0190] (Embodiment 51) The second core alloy is a magnetic material, a paramagnetic material, a ferromagnetic material, an antiferromagnetic material, or a superparamagnetic material. 41. A compact according to embodiment 39 or a sintered body according to embodiment 40.

[0191] (Embodiment 52) (a) an adiabatic rotary reactor, the reactor having an inlet port and an outlet port, each Ports are adapted to add and remove particles from the rotary reactor, respectively. Each inlet port and outlet port is optionally fitted with a particle sieve. Thermal rotary reactor; (b) a vacuum source capable of providing a vacuum to the adiabatic rotary reactor; (c) a heater capable of heating the rotary reactor during use; and optionally (d) a sampling portal that allows for the collection of samples while the device is in operation; An apparatus for mixing magnetic particles, comprising:

[0192] (Embodiment 53) 53. A system comprising the apparatus of embodiment 52, comprising: (a) A rotary water heater capable of treating solid magnetic materials with hydrogen at pressures in the range of 1 to 10 bar. elementary reactors; (b) the ability to be evacuated and heated to at least partially degas the hydrogen-containing magnetic material; One rotating degassing chamber; (c) Jet mill equipment; (d) a compression device capable of applying a force in the range of about 800 to about 3000 kN to a group of particles; The compression device is provided with a magnetic field source for applying a magnetic field, The source may be a pressure in the range of about 0.2 T to about 2.5 T while the compression device applies the force to the particle mass. the compression device capable of providing an encircling magnetic field; and (e) a sintering chamber, providing the chamber with an internal temperature in the range of about 400°C to 1200°C; while providing selective vacuum and inert atmosphere environments within the chamber. The sintering chamber In another aspect of this embodiment, the system further comprises one or more of: The sintering chamber is equipped with a magnetic field source for applying a magnetic field. In this embodiment, the system comprises two, three, four, or five of the elements (a) to (e). . [Example]

[0193] (Example) The following examples are provided to illustrate some of the concepts described within the present disclosure. Each example is to be considered as providing a specific, individual embodiment of the composition, method of making and use. However, any examples should not be construed as limitations of the more general embodiments described herein. Each of the methods described in the examples should not be construed as limiting the scope of any combination of methods within the scope of this disclosure. The present invention may be applied to the specific compositions described in the examples of these methods. The application is not limited to compositions of the present invention.

[0194] In the following examples, all materials used are to ensure accuracy with respect to numbers (e.g., amounts, temperatures, etc.). Although efforts have been made to ensure accuracy, some experimental errors and deviations should be taken into account. Unless otherwise noted, temperature is in degrees Celsius and pressure is at or near atmospheric.

[0195] Example 1 Example Process Overview

[0196] In some embodiments, the GBE-NdFeB magnets and other magnets described herein are It can be produced as follows.

[0197] The first GBM alloy is of the formula AC b R x Co y Cu d M z Based on this, some of the techniques described herein FIG. 3 illustrates various implementations of the process described herein. 1 shows a schematic diagram of an embodiment.

[0198] In some implementations, large bulk pieces of GBM alloys are melted together at 1500°C. The liquid metal was then poured into a book mold. A book or cylinder (60 mm diameter and 200 mm length) mold was produced using the same. Implementations of various sizes and shapes can be envisioned, as well as described for the GBM alloys described herein. Any composition beyond the specific compositions listed is considered within the scope of this disclosure. It can vary from 1400°C / min.

[0199] In some implementations, GBM alloys can also be prepared from molten metal by heating in an inert gas atmosphere under a 0.2 T magnetic field. The alloy is produced as a continuous series of droplets by solidification at a cooling rate of approximately 550°C / s in a jet of .

[0200] The GBM alloy can also be strip cast into thin pieces measuring 5 cm x 5 cm x 7 cm.

[0201] GBM alloys also have the potential to be highly resistant to hard magnetic material compositions in several ways as described herein. The alloy is introduced into the corresponding strip-casted thin pieces.

[0202] In some implementations, strip-cast NdFeB foils (0.2 cm x 2-6 cm x 2-8 cm) The strip casting provides a demagnetized NdFeB type flake) and a GBM alloy (5 1 cm x 5 cm x 7 cm) was subjected to hydrogen loading at different weight loadings ranging from about 0.1 to about 6.5 wt.%. In the mixing chamber, they were partially mixed together (however, the relative proportions of the two alloys were (This value is not intended to be limiting.) The thickness distribution of the strip cast section is average with a standard deviation of + / - 2.5%. The initial dimensions of the GBM flakes were again specified, with a Gaussian distribution allowed around the values. The hydrogen has a Gaussian distribution with an allowed variability of 5% across the dimensions. into the chamber at a pressure of 1000 kJ / cm, where it is absorbed by the rare earth-containing material. The hydrogen absorption process was initiated around room temperature (although other initial temperatures are clearly possible). (However, taking into account the exothermic nature of the reaction, the reaction was typically carried out for 1 to 6 hours. The bar temperature typically rose to about 80°C due to the exothermic nature of the reaction. The pressure stabilized and The reaction was considered complete once the temperature returned to ambient temperature.

[0203] In some implementations, the mixed coarse powder is then subjected to partial vacuum (<210 mbar) The resulting mixture was transferred to another rotating chamber for further mixing under 1000 kJ / min. The fine powder was then heated to 580°C for 20 hours while maintaining a partial vacuum. During the reaction, hydrogen gas was evolved from the material; once the pressure stabilized, the reaction was complete. The resulting mixed powder was discharged from the rotary reactor and passed through a 4 mesh screen. Particles that did not pass through the sieve were returned to the rotary reactor for recycling.

[0204] In some implementations, the bulk of the powder is passed through a 4 mesh screen and then The mixture was transferred to a particle homogenizer and further mixed for 45-60 minutes. The process is carried out under vacuum and / or in the presence of a protective atmosphere (argon or nitrogen) at about 30-60 revolutions per minute for 4 minutes. The test was carried out for 5 to 60 minutes. Samples were periodically removed and monitored using an inductively coupled plasma (ICP) analyzer. The composition was monitored by monitoring; if necessary, the composition was adjusted by adding additional G This was changed by adding BM alloy.

[0205] In some implementations, the powder mixture is then periodically monitored for composition by ICP. While stirring, the mixture was jetted using high-pressure nitrogen or argon as a carrier gas. The mixture was further homogenized by passing it through a mill. This resulted in a homogenization of about 1 to about 4.9 microns. Average particle size in the meter range, and 99% of the material passes through a 2500 mesh screen This resulted in a partially homogenized fine powder mixture with a particle size that allowed The powder is then returned to the particle homogenizer and subjected to partial vacuum or / and protective gas (argon or nitrogen). The mixture was mixed for an additional 45-60 minutes to achieve the final composition, which was confirmed by ICP. At the end of the mixing process, the powder is mixed with Sympatec's HELOS Hel ium-Neon L aser O ptical S system( Characterization using a particle size analyzer (He-N laser optical system) While the use of the instrument has proven useful for this purpose, other methods, e.g. Simple analysis by SEM particle counting can also be envisaged. The target properties are determined by the Average particle size of less than about 3.8 micrometers for 90% by volume of the powder and less than about 3.9 micrometers for 90% by volume of the powder. Less than chromium meters.

[0206] In some implementations, the mold is filled with the fine powder mixture at a rate of 5000 grams / minute. A magnetic field was applied so that the overall magnetic flux was 2.3 T. While the magnetic field was applied, the powder was The materials were pressed by a mechanical ram using a force ranging from about 1000 to about 2500 kN. In the final green compact, the density is about 4.3 to about 4.9 g / cm 3 in the range of, typically, 4.6 g / cm 3 The density of In some cases, the oxygen concentration inside the press was below 200 ppm. The device is controlled by hydraulic servo technology to ensure optimal precision of the applied force in the paired field. The device was designed to allow the press to produce a high degree of magnetic alignment. The weight consistency of the pressed parts was better than ±1% by weight. It was.

[0207] Optionally, the green compact is then heated to a temperature in the range of about 1050 to about 1085°C for 1 to 5 hours; typically The mixture is then subjected to a sintering heating process at about 1080° C. for 3.5 hours. In some implementations, the sintering process , during which sintering occurred, was carried out under a combination of vacuum and argon pressure.

[0208] In some implementations, this step is followed by NdFe SiO 2 , under a combination of vacuum and argon pressure. The B-type compact is heated to 800°C for 1-3 hours (typically 2.5 hours), then heated to 520°C for 1-6 hours ( Typically, a maturation / annealing treatment is performed for 3.5 hours, resulting in the The final sintered permanent magnet, called GBE-NdFeB, was obtained. The oxygen content of GBE-NdFeB based on NdFeB was generally in the range of about 500 ppm to about 2000 ppm.

[0209] Example 2 nature

[0210] In some implementations, the NdFeB-based GBE-NdFeB is shown in Figures 4A-4B. Grain boundary engineering has shown several desirable properties: In addition, the NdFeB-based GBE-NdFeB exhibited a greater resistance to demagnetization. Enhanced corrosion resistance and larger alpha and beta reversibility coefficients, representing higher resistance to corrosion. Figure 4A-B shows the ratio between two sets of sintered magnets, called "conventional magnets" and "GBE-NdFeB magnets." The conventional magnet is Nd2Fe 14 Conventional strip casting using B-rich alloys The GBE-NdFeB magnets were produced using the same starting materials as conventional magnets. Importantly, the powder mixing process described allows for the compositional variations shown in Table 1. Contains GBM alloy additions via a process. [Table 1] When comparing the magnetic properties between these two magnets, only the GBE-NdFeB magnet has a magnetic resistance higher than 20kOe. This means that the GBM alloys can be used to achieve high coercivity. A clear positive effect was demonstrated that can enhance performance, see Tables 2-6. [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7]

[0211] To further demonstrate the beneficial effects that GBM alloys can have on magnetic properties Comparative flux maturation tests were performed on magnetic materials with and without the listed GBM alloy additions. The magnetic flux of the two comparative samples was measured at various temperatures ranging from 0 to 200°C. While heating, the sintered magnet body is heated to various target temperatures and maintained at the target temperatures for 2.5 hours. After the measurement, the temperature was increased to the next data point. The magnetic characteristics of the samples are tabulated in Tables 7 and 8. The results show that the GBE-NdFeB magnets have a magnetic flux density of 1000 MPa. This shows that it is possible to have excellent magnetic performance at high temperatures with only a small reduction in In this comparison, the magnetic flux of the conventional magnets decreases by more than 20% at 120°C, while that of the GBE-NdFeB decreases by 1 % reduction, and high temperature stability can be increased by adding GBM alloys. This demonstrates that:

[0212] Table 7A shows the compositions of conventional sintered NdFeB-based magnets and GBE-NdFeB magnets, which are listed in Table 7B. The data from the flux ripening experiment is shown below, comparing the results with those from the Helmholtz coil (model number HMZ 90540, Shanghai Hengtong HT magnet Co., Ltd.) was used. [Table 8] [Table 9]

[0213] Table 8 shows the resistivity and conductivity for conventional sintered NdFeB-based magnets and GBE-NdFeB magnets. The measurement information is shown below. The comparison of the measurements shows that the GBM alloy is Nd2Fe 14 B-based strip casting material It can be seen that the resistance and conductivity of The introduction of GBM alloys increases the resistivity and decreases the conductivity. Electrical measurements were performed using an HP 4192A This was done using an LF impedance analyzer. [Table 10]

[0214] FIG. 5 shows a cross section of an induction-cast G-type alloy produced by cutting and grinding a metal plate. Examples of the microstructure of BM alloys are shown. The microstructures shown were obtained using a scanning electron microscope (SEM). The resulting microstructures were captured in backscattered electron imaging mode. Gold consists of multiple phases that appear in SEM images as varying levels of contrast. In this example, the GBM additives are, in atomic percent, Nd 8.93%, Pr 3.05%, D The composition is y 21.30%, Tb 21.16%, Co 38.33%, Cu 5.33%, Fe 1.28%, Zr 0.62%. The specific chemical compositions of the regions marked 1, 2, and 3 are shown in Table 1. are shown in Table 9. [Table 11]

[0215] Example 3 Reversible magnetic loss

[0216] The samples were placed in a permeameter where the remanence and coercivity were measured at room temperature. The temperature was increased and the sample was held at each temperature step for 5 minutes before measurement. was measured again using the well-known equation:

number

[0217] In this equation, B(T1) and iH(T1) are the remanence and intrinsic coercivity at temperature T1, respectively. B'(T0) and iH(T0) were measured at the starting temperature T0 but after cooling the sample. These are remanence and intrinsic coercivity.

[0218] In absolute terms, the grain boundary engineering process reduces the magnet strength by 70.2% at 80°C to 1% at 160°C compared to conventional magnets. GBE exhibits better (lower) (α) in the range of 80°C to 160°C, with an improvement in the range of 6% The magnets were produced (Tables 10 to 12). Furthermore, these improvements were significantly reduced (57.8 atomic % less). It should also be noted that this was observed despite the GBE magnet composition containing Dy. In this experiment, the conventional magnet showed better performance above 180°C, which was different from the GBE magnet. In comparison, this could be due to the presence of up to 75% more Dy (see Table 12). [Table 12] [Table 13] [Table 14]

[0219] As those skilled in the art will recognize, many variations of the present invention are possible in light of these teachings. Various embodiments and variations are possible, and all such are contemplated by this specification. For example, in addition to the embodiments described herein, the present invention also encompasses the The invention is based on a combination of the features of the present invention and the features of the cited prior art documents that complement the features of the present invention. The present invention contemplates and claims the resulting invention, and any described material, feature, or article is incorporated by reference in any form. It may be used in combination with other materials, features, or articles, and such combinations may be used in combination with other materials, features, or articles. It will be appreciated that this is considered to be within the scope of the invention.

[0220] Each patent, patent application, and publication cited or described in this document is hereby incorporated by reference. , each of which is incorporated herein by reference in its entirety for all purposes. The present application provides the following inventions. (Configuration 1) 1. A method for producing a sintered magnetic body having improved coercivity and remanence, comprising: a) combining a first population of particles of a first GBM alloy with a second population of particles of a second core alloy; The weight ratio of the first and second populations is in the range of about 0.1:99.9 to about 16.5:83.5, and the mixture is homogenized. forming an alloy preform; (i) the first GBM alloy has the formula: AC b R x Co y Cu d M z (In the formula, (A) AC contains Nd and Pr in an atomic ratio within the range of 0:100 to 100:0, and b is about 5 atomic % a value in the range of ∼65 atomic %; (B) R is one or more rare earth elements, and x is in the range of about 5 atomic % to about 75 atomic %. is a value within the value of; (C) Co is cobalt and Cu is copper; (D) y is a value within the range of about 20 atomic % to about 60 atomic %; (E) d is a value in the range of about 0.01 atomic % to about 12 atomic %; (F) M is at least one transition metal element other than Cu and Co, and z is about 0.01 atom. % to about 18 atomic %; and (G) The sum of b+x+y+d+z exceeds 99 atomic %. is represented by (ii) the second core alloy has a structure substantially of the formula GFe14 B (wherein G is a rare earth element) and the second core alloy is optionally doped with one or more transition metal elements or main group elements. wherein the homogenizing step is performed; (b) heating the composite alloy preform to a temperature above the solidus temperature of the first alloy but below the solidus temperature of the second core alloy; Heating to a temperature below the melting point of gold to form a population of discrete mixed alloy particles thing The method comprising: (Configuration 2) Prior to the homogenizing step (a), either the first GBM or the second core alloy, or The coarse grains of both the first GBM and the second core alloy are subjected to hydrogen treatment in the presence of hydrogen. absorption of the hydrogen into either the second core alloy or both the first GBE and the second core alloy; The method according to claim 1, wherein the treatment is carried out under conditions and for a time that allow the above. (Configuration 3) 10. The method of claim 1, wherein the homogenizing step (a) comprises multiple separate mixing steps. (Configuration 4) The homogenizing step (a) comprises a plurality of separate mixing steps, at least one of which At least one of the particle populations increases the average surface area of ​​at least one, preferably both, of the particle populations. 2. The method of claim 1, wherein (Configuration 5) 2. The method of claim 1, wherein AC is present in a range of about 10 atomic % to about 50 atomic % of the first GBM alloy. method. (Configuration 6) The atomic ratio of Nd to Pr in AC is 100:0, 25:75, 50:50, 75:25, or 0:100. The method described in Seq. 1. (Configuration 7) R is Nd, Pr, La, Ce, Gd, Ho, Er, Yb, Dy, Tb, or a combination thereof. The method described in Seq. 1. (Configuration 8) R comprises at least three different rare earth elements, totaling about 10 atoms of the first GBM alloy. % to about 60 atomic %. (Configuration 9) 10. The method of claim 1, wherein Co is present in the first GBM alloy in the range of about 30 atomic % to 40 atomic %. Law. (Configuration 10) 10. The method of claim 1, wherein Cu is present in the first GBM alloy in a range of about 0.01 atomic % to 6 atomic %. Law. (Configuration 11) M is Ag, Au, Co, Fe, Ga, Mo, Nb, Ni, Ti, V, W, Y, Zr, or a combination thereof. The method of claim 1. (Configuration 12) 10. The method of claim 1, wherein M is present in the first GBM alloy in a range of about 0.01 atomic % to 10 atomic %. Law. (Configuration 13) Nickel and / or cobalt are present in the first GBM alloy and, as a whole, the first GBM alloy 10. The method of claim 1, wherein said SiO 2 comprises at least 36 atomic % of the total composition of the GBM alloy. (Configuration 14) Iron and / or titanium are present in the first GBM alloy, and the first GBM alloy as a whole 10. The method of claim 1, wherein the gold comprises at least 2 atomic percent and up to about 6 atomic percent of the total composition. (Configuration 15) G is Nd, Pr, La, Ce, Gd, Ho, Er, Yb, Dy, Tb, or a combination thereof. The method described in Seq. 1. (Configuration 16) The first GBM alloy comprises at least neodymium, praseodymium, dysprosium, cobalt, and copper. and iron. (Configuration 17) G is Nd and / or Pr, and the second core alloy contains at least one transition metal element. or the method according to aspect 1, further doped with a main group element. (Configuration 18) G is Nd and / or Pr, and the second core alloy is Dy, Gd, Tb, Al, Co, Cu, Fe 10. The method of claim 1, further doped with one or more of Ga, Ti, or Zr. (Configuration 19) G is Nd and / or Pr, and the second core alloy contains up to 6.5 atomic % Dy, up to 3 atomic % Gd, up to 6.5 atomic % Tb, up to 1.5 atomic % Al, up to 4 atomic % Co, up to 0.5 atomic % Cu, up to 0.3 atomic % Ga, up to 0.2 atomic % Ti, up to 0.1 atomic % Zr, or is further doped with a combination thereof. (Configuration 20) the first population of particles of the first GBM alloy has an average particle size of from about 1 micron to about 4 microns; 2. The method of claim 1, wherein the range is (Configuration 21) the second population of particles of the second core alloy has an average particle size of about 2 microns to about 5 microns; 2. The method of claim 1, wherein the range is (Configuration 22) The average particle size of the group of individually separated mixed alloy particles is in the range of about 2 microns to about 6 microns. 2. The method of claim 1, wherein (Configuration 23) The heating step (b) results in particles each having a size within the range of about 1 to about 5 microns. and a core of the second core alloy having a composition defined by the elements of the first alloy. 10. The method of claim 1, which results in the formation of a population of discrete mixed alloy particles comprising a shell. . (Configuration 24) (c) subjecting the population of mixed alloy particles to magnetic field in an inert atmosphere to a common direction of magnetization. The powders are then compressed together under a magnetic field of suitable strength to align them, forming a compact. 2. The method of claim 1, comprising: (Configuration 25) 25. The method according to claim 24, wherein the compressing is performed under a force in the range of about 800 to about 3000 kN. Law. (Configuration 26) 26. The method of claim 25, wherein the magnetic field is in the range of about 0.2T to about 2.5T. (Configuration 27) forming the green compact into a sintered body comprising sintered core-shell grains held together by a grain boundary composition; the compact at at least one temperature within the range of about 800°C to about 1500°C for a time sufficient to sinter the compact. 25. The method of claim 24, further comprising heating the body. (Configuration 28) (d) In a periodic vacuum and inert gas environment, temperatures in the range of about 450°C to about 600°C. 28. The method of claim 27, further comprising heat treating the sintered body. (Configuration 29) the sintered particles of the second core alloy having a size within the range of about 0.3 to about 2.9 microns. 28. The method of embodiment 27, comprising a core. (Configuration 30) The sintered core-shell particle further comprises a quasi-concentric shell surrounding the core, the shell comprising The composition is defined by a shell layer of Co, Cu, and M elements within the matrix of the second core alloy. 30. The method of claim 29, wherein (Configuration 31) In the grain boundary alloy, cobalt and copper are enriched relative to their presence in the sintered grains. 28. The method of claim 27, wherein (Configuration 32) The grain boundary alloy contains cobalt and copper at least in part relative to the total composition of the alloy as measured by EDS. and at least three rare earth elements and one transition element in a total amount of 20% by weight. 28. The method of claim 27, wherein each comprises no more than 10 wt.% of the total alloy composition. (Configuration 33) 10. The method of claim 1, wherein the overall chemical composition of the alloy or particles is determined by ICP. (Configuration 34) The overall chemical composition within the grain or within the grain boundary can be determined by EDS mapping across the fractured or polished surface. 28. The method of claim 1, 24, or 27, wherein the identification is performed using ping. (Configuration 35) 2. A particle or population of particles produced by the method of claim 1. (Configuration 36) 25. A powder compact produced by the method of claim 24. (Configuration 37) 28. A sintered body produced by the method according to aspect 27. (Configuration 38) A device comprising the sintered body according to configuration 37, Head actuators for hard disks, erasing heads, magnetic resonance imaging (MRI) equipment, magnetic rods books, magnetic fasteners, speakers, headphones or earphones, mobile phones and other household appliances Garden appliances, magnetic bearings and magnetic couplings, NMR spectrometers, electric motors (e.g. , Cordless tools, Servo motors, Compression motors, Synchronous motors, Spindle motors and stepping motors, electric steering and power steering, hybrid such as those used in drive motors for motorized and electric vehicles), and generators ( The device is selected from the group consisting of: a wind turbine. (Configuration 39) Formula:AC b R x Co y Cu d M z(In the formula: (A) AC contains Nd and Pr in an atomic ratio within the range of 0:100 to 100:0, and b is about 5 atomic % to a value in the range of about 65 atomic percent; (B) R is one or more rare earth elements, and x is in the range of about 5 atomic % to about 75 atomic %. is a value; (C) Co is cobalt and Cu is copper; (D) y is a value within the range of about 20 atomic % to about 60 atomic %; (E) d is a value in the range of about 0.01 atomic % to about 12 atomic %; (F) M is at least one transition metal element excluding Cu and Co, and z is about 0.01 atoms. % to about 18 atomic %; and (G) b+x+y+d+z exceeds one or more of 95, 98, 99, 99.5, 99.8, or 99.9 atomic % (up to about 99.9 atomic % or 100 atomic % and A composition containing less than 0.1% by weight of oxygen or carbon. (Configuration 40) The atomic ratio of Nd to Pr in AC is 100:0, 25:75, 50:50, 75:25, or 0:100. The composition described in 39. (Configuration 41) 39. The method according to claim 39, wherein R is La, Ce, Gd, Ho, Er, Yb, Dy, Tb, or a combination thereof. Composition of. (Configuration 42) M is Ag, Au, Co, Fe, Ga, Mo, Nb, Ni, Ti, V, W, Y, Zr, or a combination thereof. 40. The composition according to claim 39. (Configuration 43) The alloy substantially has the formula (Nd 0.01-0.18 Pr 0.01-0.18 Dy 03-0.5 Tb 0.3-0.5 ) aa (Co0.85-0.9 5Cu 0.04-0.15 Fe 0.01-0.08 ) bb (Zr 0.00-1.00 ) cc ; (In the formula: aa is a value within the range of 42 atomic % to 75 atomic %; bb is a value in the range of 6 atomic % to 60 atomic %; and cc is a value in the range of 0.01 atomic % to 18 atomic %; However, the total amount of Nd+Pr is more than 12 atomic %; However, the total amount of Nd+Pr+Dy+Tb is 95, 98, 99, 99.5, 99.8, or 99.9 atomic %. at least one of more than about 99.9 or 100 atomic %; However, the total amount of Co+Cu+Fe exceeds 95, 98, 99, 99.5, 99.8, or 99.9 atomic % and is approximately up to 99.9 or 100 atomic %; and However, aa+bb+cc is greater than 0.995 and up to about 0.999 or 1. 40. The composition according to claim 39, wherein (Configuration 44) The alloy is (Nd 0.16 Pr 0.05 Dy 0.392 Tb 0.40 ) aa (Co 0.86 Cu 0.12 Fe 0.02 ) bb (Zr 1.00 ) cc of Described by a stoichiometric formula, any individual variation in the values ​​in parentheses is independent and within ±0.01, 44. The composition of claim 43, wherein the variance is ±0.02, ±0.04, ±0.06 ±0.0.8, or ±0.1. (Configuration 45) the first population of particles of the first GBM alloy has an average particle size of about 1 micron to about 4 microns; 40. The composition of claim 39, wherein the composition is within the range of (Configuration 46) 40. The composition according to claim 39, which is in a form containing columnar and spherical crystallites. (Configuration 47) 40. The composition of claim 39, wherein the composition is in amorphous form. (Configuration 48) The second core alloy is a magnetic material, a paramagnetic material, a ferromagnetic material, an antiferromagnetic material, or a superparamagnetic material. 38. The sintered body according to claim 37. (Configuration 49) 1. An apparatus for mixing magnetic particles, comprising: (a) an adiabatic rotary reactor, the reactor having an inlet port and an outlet port, each Ports are adapted to add and remove particles from the rotary reactor, respectively. Each inlet port and outlet port is optionally fitted with a particle sieve. Thermal rotary reactor; (b) a vacuum source capable of providing a vacuum to the adiabatic rotary reactor; (c) a heater capable of heating the rotary reactor during use; and optionally (d) a sampling portal that allows for the collection of samples while the device is in operation; The device comprising: (Configuration 50) 50. A system comprising the apparatus of claim 49: (a) A rotary water heater capable of treating solid magnetic materials with hydrogen at pressures in the range of 1 to 10 bar. elementary reactors; (b) capable of being evacuated and heated to at least partially degas the hydrogen-containing magnetic material; Rotating degassing chamber; (c) Jet mill equipment; (d) a compression device capable of applying a force in the range of about 800 to about 3000 kN to a group of particles; The compression device has a magnetic field source attached thereto, and the magnetic field source providing a magnetic field in the range of about 0.2 T to about 2.5 T while applying the pressure to the particle population. the compression device; and (e) a sintering chamber, providing the chamber with an internal temperature in the range of about 400°C to 1200°C; while providing selective vacuum and inert atmosphere environments within the chamber. the sintering chamber; The system further comprises one or more of:

Claims

1. Formula AC b R x Co y Cu d M z (In the formula, (A) AC contains Nd and Pr in an atomic ratio ranging from 0:100 to 100:0, and b is a value ranging from 10 atomic % to 50 atomic %; (B) R is one or more rare earth elements including one or both of Tb and Dy, and x is a value within the range of 10 atomic % to 60 atomic %; (C) Co is cobalt and Cu is copper; (D) y is a value within the range of 30 atomic % to 40 atomic %; (E) d is a value in the range of 0.01 atomic % to 6 atomic %; (F) M is at least one transition metal element excluding Cu and Co, and z is a value within the range of 0.01 atomic % to 10 atomic %; (G) b+x+y+d+z is greater than one or more of 95, 98, 99, 99.5, 99.8, or 99.9 atomic % up to 99.9 atomic % or 100 atomic % A sintered body or device comprising a GBM alloy represented by the GBM alloy contains less than 0.1 wt. % oxygen or less than 0.1 wt. % carbon; and The sintered body or device as described above, wherein the sintered body is a magnet.

2. the atomic ratio of Nd to Pr in AC is 100:0, 25:75, 50:50, 75:25, or 0:100; or R is La, Ce, Gd, Ho, Er, Yb, Dy, Tb, or a combination thereof; or 2. The sintered body or device of claim 1, wherein M is Ag, Au, Fe, Ga, Mo, Nb, Ni, Ti, V, W, Y, Zr, or a combination thereof.

3. The GBM alloy has a structure substantially of the formula (Nd 0.01-0.18 Pr 0.01-0.18 Dy 0.3-0.5 Tb 0.3-0.5 ) aa (Co 0.85-0.95 Cu 0.04-0.15 Fe 0.01-0.08 ) bb (Zr 0.00-1.00 ) cc ; (In the formula, aa is a value in the range of 42 atomic % to 75 atomic %; bb is a value in the range of 6 atomic % to 60 atomic %; and cc is a value in the range of 0.01 atomic % to 18 atomic %; However, the total amount of Nd+Pr is more than 12 atomic percent; provided that the total amount of Nd+Pr+Dy+Tb is greater than at least one of 95, 98, 99, 99.5, 99.8, or 99.9 atomic % up to 99.9 or 100 atomic %; provided that the total amount of Co+Cu+Fe is greater than 95, 98, 99, 99.5, 99.8, or 99.9 atomic % up to 99.9 or 100 atomic %; and However, aa+bb+cc must exceed 0.995 and be up to 0.999 or 1.

3. The sintered body or device according to claim 2, wherein

4. The GBM alloy is (Nd 0.16 Pr 0.05 Dy 0.392 Tb 0.40 ) aa (Co 0.86 Cu 0.12 Fe 0.02 ) bb (Zr 1.00 ) cc wherein any individual variation in the values ​​within the arcs is independently ±0.01, ±0.02, ±0.04, ±0.06, ±0.08, or ±0.

1.

5. the first population of particles of the GBM alloy has an average particle size in the range of 1 micron to 4 microns; or The sintered body or device comprises a composition having a morphology containing columnar crystals and spherical crystallites; or The sintered body or device comprises a composition in amorphous form; The sintered body or device according to claim 1.

6. 2. The sintered body or device of claim 1, wherein the GBM alloy is magnetic, paramagnetic, ferromagnetic, antiferromagnetic, or superparamagnetic.

7. 2. The sintered body or device according to claim 1, wherein the magnet is a Nd-B-Fe magnet.

8. The atomic ratio of Nd to Pr in AC is 100:0, 25:75, 50:50, 75:25, or 0:

100. The sintered body or device according to claim 1.

9. The sintered body or device of claim 1, wherein R comprises at least three different rare earth elements.

10. 2. The sintered body or device of claim 1, wherein M is Ag, Au, Fe, Ga, Mo, Nb, Ni, Ti, V, W, Y, Zr, or a combination thereof.

11. The sintered body or device of claim 1, wherein iron and / or titanium are present in the GBM alloy and collectively account for at least 2 atomic percent and at most 6 atomic percent of the total composition of the GBM alloy.

12. The sintered body or device has a structure of formula G 2 Fe 14 B, where G is a rare earth element; 10. The body or device of claim 1, wherein the second GBM alloy is optionally doped with one or more transition metal or main group elements.

13. 13. The body or device of claim 12, wherein G is Nd, Pr, La, Ce, Gd, Ho, Er, Yb, Dy, Tb, or a combination thereof.

14. 10. The body or device of claim 1, wherein the GBM alloy comprises at least neodymium, praseodymium, dysprosium, cobalt, copper, and iron.

15. 13. The body or device of claim 12, wherein G is Nd and / or Pr, and the second GBM alloy is further doped with at least one transition metal element or main group element.

16. 13. The body or device of claim 12, wherein G is Nd and / or Pr, and the second GBM alloy is further doped with one or more of Dy, Gd, Tb, Al, Co, Cu, Fe, Ga, Ti, or Zr.

17. 13. The body or device of claim 12, wherein G is Nd and / or Pr, and the second GBM alloy is further doped with up to 6.5 atomic % Dy, up to 3 atomic % Gd, up to 6.5 atomic % Tb, up to 1.5 atomic % Al, up to 4 atomic % Co, up to 0.5 atomic % Cu, up to 0.3 atomic % Ga, up to 0.2 atomic % Ti, up to 0.1 atomic % Zr, or combinations thereof.

18. the first population of particles of the GBM alloy has an average particle size in the range of 1 micron to 4 microns; or 13. The body or device of claim 12, wherein the second population of particles of the second GBM alloy has an average particle size in the range of 2 microns to 5 microns.

19. the sintered body or device comprises a population of individually separated mixed alloy particles; each particle comprising a core of a second GBM alloy having a size in the range of 1 to 5 microns and a shell whose composition is defined by the elements of said GBM alloy; and 10. The sintered body or device of claim 1, wherein the average particle size of the population of individually separated mixed alloy particles is in the range of 2 microns to 6 microns.

20. the sintered body or device comprises a population of individually separated mixed alloy particles; each particle comprising a core of a second GBM alloy having a size in the range of 1 to 5 microns and a shell whose composition is defined by the elements of said GBM alloy; and 2. The sintered body or device of claim 1, wherein the average particle size of the population of individually separated mixed alloy particles is in the range of 0.3 microns to 2.9 microns.

21. 20. The sintered body or device of claim 19, wherein the sintered core-shell particle further comprises a quasi-concentric shell surrounding the core, the shell being compositionally defined by a shell layer of Co, Cu, and M elements within a matrix of the second GBM alloy.

22. 21. The sintered body or device of claim 20, wherein the sintered core-shell particle further comprises a quasi-concentric shell surrounding the core, the shell being compositionally defined by a shell layer of Co, Cu, and M elements within a matrix of the second GBM alloy.

23. the GBM alloy is enriched in cobalt and copper; or 16. The sintered body or device of claim 15, wherein the GBM alloy comprises cobalt and copper in a combined amount of at least 20 wt.% of the total alloy composition as determined by EDS, and at least three rare earth elements and one transition element, each not exceeding 10 wt.% of the total alloy composition.

24. 10. The body or device of claim 1, wherein the overall chemical composition of the GBM alloy is characterized by ICP.

Images