AND STRUCTURES OBTAINED THEREFROM

PRIORITY DATA

[0001] This patent application is an international application claiming priority to U.S. Patent App. No. 63/061,798, filed on August 6, 2020, U.S. Patent App. No. 63/061,800, filed on August 6, 2020, and U.S. Patent App. No. 17/359,557, filed on June 26, 2021, each of which is hereby incorporated by reference herein.

FIELD OF THE INVENTION

[0002] The present invention generally relates to methods for tailoring magnetic properties in various types of magnets, and magnetic structures obtained therefrom.

BACKGROUND OF THE INVENTION

[0003] A magnet is a material or object that produces a magnetic field. The magnetic field creates a force that acts on other magnets or ferromagnetic materials, such as iron, steel, nickel, or cobalt. A permanent magnet is an object made from a material that is magnetized and creates its own persistent magnetic field.

[0004] Although ferromagnetic and ferrimagnetic materials are the only materials attracted to a magnet strongly enough to be commonly considered magnetic, all substances respond at least weakly to a magnetic field. Some ferromagnetic materials are magnetically soft materials (“soft magnets”) such as annealed iron. Soft magnets can be magnetized but do not tend to stay magnetized. On the other hand, magnetically hard materials (“hard magnets”) tend to stay magnetized and are typically difficult to demagnetize. Permanent magnets are commonly made from hard ferromagnetic materials such as alnico alloys and ferrite that are subjected to special processing in a strong magnetic field during manufacture to align the internal microcrystalline structure, making the materials very hard to demagnetize. Demagnetizing a saturated magnet requires application of a magnetic field whose minimum strength correlates with the magnetic coercivity of the magnet. Hard magnets have high magnetic coercivity, while soft magnets have relatively low magnetic coercivity.

[0005] Applications of permanent magnets include, but are not limited to, electric vehicle motors, electric take-off assist motors and sensors, magnetic separators, and magnetic detectors. Applications of soft magnets include transformer cores, motors, generators, inductors, and electromagnets.

[0006] Magnetic anisotropy describes how an object’s magnetic properties can be different depending on direction. When there is no preferential direction for an object’s magnetic moment, the object will respond to an applied magnetic field in the same way, regardless of which direction the field is applied. This is known as magnetic isotropy. In contrast, magnetically anisotropic materials will be easier or harder to magnetize depending on which way the object is rotated. For many magnetically anisotropic materials, there are at least two easiest directions to magnetize the material, which are a 180° rotation apart. The line parallel to these directions is called the magnetic easy axis and is an energetically favorable direction of spontaneous magnetization.

[0007] Magnetocrystalline anisotropy has a great influence on industrial uses of ferromagnetic materials. Materials with high magnetic anisotropy usually have high magnetic coercivity — that is, they are hard to demagnetize. These are called hard ferromagnetic materials and are used to make permanent magnets. For example, the high anisotropy of rare-earth metals is mainly responsible for the strength of rare- earth magnets. During manufacture of magnets, a powerful magnetic field aligns the microcrystalline grains of the metal such that their easy axes of magnetization all point in the same direction, freezing a strong magnetic field into the material.

[0008] Nearly uniform orientation of a crystal structure aligns the easy axis of each grain, allowing the material to be easily magnetized with a small orientation distribution and giving the material a high resistance to uniform demagnetizing fields. Resistance to demagnetization has been increased in the art by manipulating processdependent microstructure and chemistry to optimize competing mechanisms in generating high-energy products. However, in applications such as electric motors, generated magnetic fields interact non-uniformly with magnetic materials. Because fields generated are non-uniformly concentrated to regions of high and low magnetic flux density, regions such as comers and surfaces of the magnet are highly susceptible to demagnetization. In addition, the corners are inherently susceptible to demagnetization even in with uniform flux, due to the magnet geometry and microstructure. The magnetic field angle of incidence in these regions can vary significantly away from the angles producing maximal torque and lead to demagnetization, thereby limiting the achievable weight and volume efficiencies of the magnetic material.

[0009] State-of-the-art bulk permanent magnet materials (e.g. NdFeB) with anisotropic crystallographic texture have desirable magnetic performance in comparison to isotropic variants. Anisotropic materials are conventionally produced by die-press and sintering methods in which consolidation of powder precursors produces a relatively uniform texture throughout the material. Heat treatment in a magnetic field then produces relatively uniform magnetic alignment of all grains in the material. The die-press and sinter methods are significantly constrained to prismatic geometries and uniaxial textures, and therefore limited in their ability to achieve desirable crystallographic textures and magnetic shapes.

[0010] The benefits of easy axis alignment through texturing in permanent magnets are well-known. See Dulis et al., “Solid NdFeB Magnets Made by Gas Atomization and Extrusion”, Science and Technology of Nanostructured Magnetic Materials, 1991, pages 599-606; and White et al., “Net shape processing of alnico magnets by additive manufacturing”, IEEE Transactions on Magnetics, 53.11 (2017): 1-6. Some methods of texture control in NdFeB are based on plastic deformation of a consolidated material. In this technique, the crystallographic orientation is largely uniform in the extrusion direction (e.g. c-axis for NdFeB permanent magnets) with limited ability to control the texture in orientations other than the direction of plastic deformation. Directional solidification is alternatively used to produce uniaxial texture, but texture in these methods is uniaxial and dependent on the maximum thermal gradient. Directional solidification is severely limited in two ways. First, texture in the preferred growth direction, in the case of NdFeB, produces a preferred growth orientation [100] orthogonal to the easy axis direction which is the [001] c- axis in NdFeB. Second, these methods produce long columnar grains well above the single-domain limit for these materials, thus limiting the achievable coercivity. See Ma et al., “The impact of the directional solidification on the magnetic properties of NdFeB magnets”, Journal of applied physics 70.10 (1991): 6471-6473.

[0011] Current methods to additively manufacture permanent magnets are limited to those easily processible by liquid-processing methods and very limited in achievable performance for higher-energy-product NdFeB materials where microstructures are heavily optimized for die-press methods. See Kolb et al., “Laser Beam Melting of NdFeB for the production of rare-earth magnets”, 20166th International Electric Drives Production Conference (EDPC), IEEE, 2016 and Jacimovic et al., “Net shape 3D printed NdFeB permanent magnet”, preprint arXiv: 1611.05332 [physics. ins-det] (2016).

[0012] Control of crystallographic texture in directed energy deposition (DED) manufacturing using external magnetic fields to alter crystal texture in structural alloys has been described in academic studies. See Wang et al., “Texture control of Inconel 718 superalloy in laser additive manufacturing by an external magnetic field”, Journal of materials science 54.13 (2019): 9809-9823; and Wang et al., “Effect of External Magnetic Field on the Microstructure of 316L Stainless Steel Fabricated by Directed Energy Deposition”, Proceedings of the ASME 2019 International Mechanical Engineering Congress and Exposition, Volume 2B: Advanced Manufacturing (2019). While DED using powder spray or wires produces parts with less geometric constraints than traditional methods, these parts usually need extensive finishing procedures due to a poor surface finish after deposition has occurred. This is in contrast to powder bed-based processes which can produce near- net-shape parts after deposition.

[0013] The current methods are inherently limited to microstructures achieved in the unique thermoprocessing conditions of conventional additive manufacturing (columnar grains greater than 100 pm in length), which limits the magnetic performance. [0014] New or improved methods, structures, and systems are desired for tailoring magnetism in hard or soft magnetic materials.

SUMMARY OF THE INVENTION

[0015] The present invention addresses the aforementioned needs in the art, as will now be summarized and then further described in detail below.

[0016] Some variations provide a method of making a magnet with tailored magnetism, the method comprising:

(a) providing a feedstock composition containing one or more magnetic or magnetically susceptible materials;

(b) exposing a first amount of the feedstock composition to an energy source for melting in a scan direction, thereby generating a first melt layer;

(c) solidifying the first melt layer in the presence of an externally applied magnetic field, thereby generating a magnetic metal layer containing a plurality of individual voxels;

(d) optionally repeating steps (b) and (c) a plurality of times to generate a plurality of solid layers by sequentially solidifying a plurality of melt layers in a build direction, thereby generating a plurality of magnetic metal layers; and

(e) recovering a magnet comprising the magnetic metal layer, wherein the externally applied magnetic field has a magnetic-field orientation, defined with respect to the scan direction, that is selected to control (i) a magnetic axis within the magnetic metal layer and/or (ii) a crystallographic texture within the magnetic metal layer.

[0017] The magnetic or magnetically susceptible materials in the feedstock composition may include elemental metals, metal alloys, ceramics, metal matrix composites, or combinations thereof, for example. The feedstock composition may be in the form of a powder, a wire, or a combination thereof, for example.

[0018] In some embodiments, the magnetic-field orientation is selected to control the crystallographic texture but not necessarily the magnetic axis within the magnetic metal layer. In some embodiments, the magnetic-field orientation is selected to control the magnetic axis but not necessarily the crystallographic texture within the magnetic metal layer. In preferred embodiments, the magnetic-field orientation is selected to control both the crystallographic texture as well as the magnetic axis within the magnetic metal layer.

[0019] The energy source may be a laser beam, an electron beam, or a combination thereof. The energy source preferably imposes a thermal gradient that melts a portion of the feedstock composition in a scan direction, rather than bulk melting the entire feedstock composition. In some embodiments, steps (b) and (c) utilize a technique selected from the group consisting of selective laser melting, electron beam melting, laser engineered net shaping, selective laser sintering, direct metal laser sintering, integrated laser melting with machining, laser powder injection, laser consolidation, direct metal deposition, directed energy deposition, plasma arcbased fabrication, ultrasonic consolidation, electric arc melting, and combinations thereof.

[0020] Steps (b) and (c) together may be referred to additive manufacturing or welding. When step (d) is employed to generate a plurality of solid layers by sequentially solidifying a plurality of melt layers in a build direction, then steps (b) and (c) together are typically referred to as additive manufacturing or 3D printing. [0021] In some preferred embodiments, the magnetic-field orientation is adjusted during step (c), i.e. during solidification of the first melt layer. For example, after some voxels have been formed in a first melt layer, the magnetic-field orientation may be adjusted, after which more voxels are formed in the first melt layer.

[0022] In some embodiments, step (b) is also conducted in the presence of the externally applied magnetic field. Optionally, the magnetic-field orientation may be adjusted during step (b).

[0023] When step (d) is conducted, to generate a plurality of solid layers by sequentially solidifying a plurality of melt layers in a build direction, the magnetic- field orientation may be adjusted in the build direction.

[0024] In some embodiments, the individual voxels are defined by a characteristic voxel length scale selected from about 50 microns to about 1000 microns. In certain embodiments, the characteristic voxel length scale is selected from about 100 microns to about 500 microns. The individual voxels may be larger than an average grain size within the magnetic metal layer.

[0025] In some embodiments, the magnetic-field orientation is selected to control voxel-specific magnetic axes within the plurality of individual voxels contained within the magnetic metal layer. In these or other embodiments, the magnetic-field orientation is selected to control voxel-specific crystallographic textures within the plurality of individual voxels contained within the magnetic metal layer. In some embodiments, the magnetic-field orientation may be selected to control voxel-specific magnetic easy axes within the plurality of individual voxels contained within the magnetic metal layer.

[0026] In some embodiments, the individual voxels are substantially magnetically aligned with each other. In these or other embodiments, the individual voxels are each characterized by a magnetic easy axis that is substantially aligned across the plurality of individual voxels.

[0027] In some preferred embodiments, the magnetic-field orientation is selected to control voxel-specific magnetic axes as well as voxel-specific magnetic easy axes within the plurality of individual voxels contained within the magnetic metal layer, wherein the voxel-specific magnetic axes are substantially aligned with the voxel-specific magnetic easy axes for at least a portion of the magnetic metal layer. In certain embodiments, the voxel-specific magnetic axes are substantially aligned with the voxel-specific magnetic easy axes for all of the magnetic metal layer. [0028] In other embodiments, the magnetic-field orientation is selected to control voxel-specific magnetic axes as well as voxel-specific magnetic easy axes within the plurality of individual voxels contained within the magnetic metal layer, wherein the voxel-specific magnetic axes are configured to be at angles with the voxel-specific magnetic easy axes for at least a portion of the magnetic metal layer. [0029] In some methods, conditions in step (b) and/or step (c) are controlled such that thermal gradients assist in generating the crystallographic texture within the magnetic metal layer.

[0030] In some embodiments, different feedstock compositions, each comprising one or more magnetic or magnetically susceptible materials, are exposed to the energy source, and the crystallographic texture is adjusted during the method by performing step (b), step (c), and optionally step (d) at different times using the different feedstock compositions. Different feedstock compositions may be different concentrations of the same components.

[0031] In some methods, the magnet is a permanent magnet with tailored magnetism. For example, a permanent magnet may be selected from the group consisting of a NdFeB magnet, a NdDyFeB magnet, a FeCoCr magnet, a FeAlNiCo magnet, a SmCo magnet, and combination thereof.

[0032] Some variations of the invention provide a method of making a magnet with tailored magnetism by additive manufacturing, the method comprising:

(a) providing a feedstock composition containing base particles and one or more surface-modifying particles that are chemically and/or physically disposed on surfaces of the base particles, wherein the surface-modifying particles are magnetic or magnetically susceptible;

(b) exposing a first amount of the feedstock composition to an energy source for melting in a scan direction, thereby generating a first melt layer;

(c) solidifying the first melt layer in the presence of an externally applied magnetic field, thereby generating a magnetic metal layer containing a plurality of individual voxels;

(d) optionally repeating steps (b) and (c) a plurality of times to generate a plurality of solid layers by sequentially solidifying a plurality of melt layers in a build direction, thereby generating a plurality of magnetic metal layers; and

(e) recovering a magnet comprising the magnetic metal layer, wherein the externally applied magnetic field has a magnetic-field orientation, defined with respect to the scan direction, that is selected to control a magnetic axis within the magnetic metal layer.

[0033] In some embodiments, the energy source is a laser beam, an electron beam, or a combination thereof. Steps (b) and (c) may utilize a technique selected from the group consisting of selective laser melting, electron beam melting, laser engineered net shaping, selective laser sintering, direct metal laser sintering, integrated laser melting with machining, laser powder injection, laser consolidation, direct metal deposition, directed energy deposition, plasma arc-based fabrication, ultrasonic consolidation, electric arc melting, and combinations thereof, for example. [0034] In some preferred embodiments, the magnetic-field orientation is adjusted during step (c), i.e. during solidification of the first melt layer. For example, after some voxels have been formed in a first melt layer, the magnetic-field orientation may be adjusted, after which more voxels are formed in the first melt layer.

[0035] In some embodiments, step (b) is also conducted in the presence of the externally applied magnetic field, along with step (c). Optionally, the magnetic-field orientation may be adjusted during step (b).

[0036] When step (d) is conducted, the magnetic-field orientation may be adjusted in the build direction.

[0037] In some embodiments, the magnetic-field orientation is selected to control a crystallographic texture within the magnetic metal layer.

[0038] In some embodiments, during step (c), the surface-modifying particles are substantially magnetically aligned with each other. In these or other embodiments, during step (c), the surface-modifying particles nucleate growth of grains that are magnetically aligned with each other.

[0039] The base particles may be metals, metal alloys, ceramics, carbon, polymers, or combinations thereof, for example, and are not necessarily magnetic or magnetically susceptible. In certain embodiments, the base particles are magnetic or magnetically susceptible.

[0040] In some embodiments, the surface-modifying particles are ferromagnetic. In these or other embodiments, the surface-modifying particles nucleate growth of grains that are ferromagnetic.

[0041] In some embodiments, the surface-modifying particles have an average particles size of 10 microns or less, such as an average particles size of 1 micron or less. The surface-modifying particles may be spherical, non-spherical (e.g., pyramidal or cubic), or random in shape.

[0042] In some embodiments, the individual voxels are defined by a characteristic voxel length scale selected from about 50 microns to about 1000 microns. In certain embodiments, the characteristic voxel length scale is selected from about 100 microns to about 500 microns. The individual voxels may be larger than an average grain size within the magnetic metal layer. [0043] In some embodiments, the magnetic-field orientation is selected to control voxel-specific magnetic axes within the plurality of individual voxels contained within the magnetic metal layer. In these or other embodiments, the magnetic-field orientation is selected to control voxel-specific crystallographic textures within the plurality of individual voxels contained within the magnetic metal layer. In certain embodiments, the magnetic-field orientation is selected to control voxel-specific magnetic easy axes within the plurality of individual voxels contained within the magnetic metal layer.

[0044] In some embodiments, the individual voxels are substantially magnetically aligned with each other.

[0045] In some embodiments, the individual voxels are each characterized by a magnetic easy axis that is substantially aligned across the plurality of individual voxels.

[0046] In certain embodiments, the magnetic-field orientation is selected to control voxel-specific magnetic axes as well as voxel-specific magnetic easy axes within the plurality of individual voxels contained within the magnetic metal layer, wherein the voxel-specific magnetic axes are substantially aligned with the voxelspecific magnetic easy axes for at least a portion of the magnetic metal layer. The voxel-specific magnetic axes may be substantially aligned with the voxel-specific magnetic easy axes for all of the magnetic metal layer.

[0047] In other embodiments, the magnetic-field orientation is selected to control voxel-specific magnetic axes as well as voxel-specific magnetic easy axes within the plurality of individual voxels contained within the magnetic metal layer, wherein the voxel-specific magnetic axes are configured to be at angles with the voxel-specific magnetic easy axes for at least a portion of the magnetic metal layer. [0048] In some methods, conditions in step (b) and/or step (c) are controlled such that thermal gradients assist in generating the crystallographic texture within the magnetic metal layer.

[0049] Optionally, different feedstock compositions, each comprising one or more magnetic or magnetically susceptible surface-modifying particles, are exposed to the energy source, and the crystallographic texture is adjusted during the method by performing step (b), step (c), and optionally step (d) at different times using the different feedstock compositions.

[0050] The magnetic metal layer may be characterized by a microstructure with equiaxed grains. In some embodiments, the magnetic metal layer is characterized by a crack-free microstructure.

[0051] In some methods, the additively manufactured magnet is a permanent magnet, such as a NdFeB magnet, a NdDyFeB magnet, a FeCoCr magnet, a FeAlNiCo magnet, a SmCo magnet, or a combination thereof.

[0052] In other methods, the additively manufactured magnet is a nonpermanent magnet, such as a soft magnet.

BRIEF DESCRIPTION OF THE FIGURES

[0053] FIG. 1 depicts a conventional isotropic magnet (left side) and a conventional anisotropic magnet (right side).

[0054] FIG. 2 depicts a magnet with a magnetic field applied in three different directions within three regions.

[0055] FIG. 3 depicts a magnet with a magnetic field in three different directions in three regions, with the crystallographic orientation controlled through thermal gradients in solidification.

[0056] FIG. 4 is a schematic set-up of additive manufacturing with electromagnets that are not magnetically active (electrical current is off).

[0057] FIG. 5 is a schematic set-up of additive manufacturing with electromagnets that are magnetically active (electrical current is on), creating an applied magnetic field.

[0058] FIG. 6 is a schematic set-up of additive manufacturing with electromagnets that are magnetically active (electrical current is on) and disposed at an angled orientation, creating an applied magnetic field that is at an angle with respect to the additive-manufacturing build layer. [0059] FIG. 7 shows photomicrographs of the NchFeuB magnet microstructure with a shifted dendrite growth direction against the direction of maximum thermal gradient, in the Example.

[0060] FIG. 8 shows a photomicrograph top view of the laser-welded Nd2Fei4B magnet structure, in the Example.

[0061] FIG. 9 shows the increase in NdFeB easy axis [001] texture along the scan vector direction in IPF density plots, in the Example. EBSD maps are provided for reference orientations.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

[0062] The methods, structures, compositions, and systems of the present invention will be described in detail by reference to various non-limiting embodiments.

[0063] This description will enable one skilled in the art to make and use the invention, and it describes several embodiments, adaptations, variations, alternatives, and uses of the invention. These and other embodiments, features, and advantages of the present invention will become more apparent to those skilled in the art when taken with reference to the following detailed description of the invention in conjunction with the accompanying drawings.

[0064] As used in this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly indicates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art to which this invention belongs.

[0065] Unless otherwise indicated, all numbers expressing conditions, concentrations, dimensions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending at least upon a specific analytical technique. [0066] The term “comprising,” which is synonymous with “including,” “containing,” or “characterized by” is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. “Comprising” is a term of art used in claim language which means that the named claim elements are essential, but other claim elements may be added and still form a construct within the scope of the claim. [0067] As used herein, the phrase “consisting of’ excludes any element, step, or ingredient not specified in the claim. When the phrase “consists of’ (or variations thereof) appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole. As used herein, the phrase “consisting essentially of’ limits the scope of a claim to the specified elements or method steps, plus those that do not materially affect the basis and novel characteristic(s) of the claimed subject matter.

[0068] With respect to the terms “comprising,” “consisting of,” and “consisting essentially of,” where one of these three terms is used herein, the presently disclosed and claimed subject matter may include the use of either of the other two terms, except when used in Markush groups. Thus in some embodiments not otherwise explicitly recited, any instance of “comprising” may be replaced by “consisting of’ or, alternatively, by “consisting essentially of.”

[0069] The present invention, in some variations, is predicated on new methods for tailoring magnetism in hard or soft magnetic materials. In particular, methods are disclosed to individually tailor three-dimensional voxels to have selected crystallographic orientations and, independently, selected magnetic orientations with location specificity of both crystallographic orientations and magnetic orientations throughout a magnet.

[0070] Some embodiments of the invention enable control of solidification of additively manufactured or welded microstructures on the order of the single domain limit (e.g., about 1-5 pm) to maximize the resistance to demagnetization in addition to controlling the orientation of the easy axis (or at least one easy axis when there are more than one). Certain embodiments utilize the advantages of easy-axis alignment in magnet regions of interest (e.g. surfaces or corners) in order to improve overall resistance to demagnetization in a bulk magnet. Certain embodiments increase the total energy product of additively manufactured or welded magnets by controlling fields to manipulate solidification.

[0071] Some variations provide methods for fabrication of bulk magnetic materials with selective regions exhibiting different, and tailorable, magnetic alignments. By manufacturing a magnet additively, with melting and solidification in each layer taking place voxel by voxel, such as via a site-specific energy source (e.g., a laser beam or an electron beam), the magnetic orientation of each voxel may be independently aligned. Independent voxel alignment may be achieved by applying a magnetic field during additive manufacturing — specifically, during the cooling processes (including solidification and solid-state transformations) of each voxel. The magnetic orientation of each voxel may be set independently of all other voxels, if desired.

[0072] In some embodiments, the magnetic orientations are arranged in order to create fields having certain regions of concentrated magnetic flux. These embodiments are beneficial to resist demagnetization in certain regions, or to optimize air-gap magnetic flux in the case of torque generation for motors, for example. Near sharp geometric features (e.g., edges), high flux densities may be encountered at non- optimal angles, causing nucleation of a reverse domain that leads to partial or complete demagnetization of the magnet. In order to resist this early demagnetization, orientation of the magnetic alignment may be selected or adjusted to optimize the angle between crystallographic and magnetic orientations of susceptible regions. Some embodiments consider the Wigner-Seitz angular dependency of magnetic coercivity. Advantages of some embodiments include the possibility of utilizing stronger external fields as well as higher temperatures.

[0073] Also, current manufacturing methods (e.g. press and sinter methods) are inherently limited in geometries by the shape of the die (often prismatic) and eventual loss of net shape due to shrinkage during sintering. By contrast, additive manufacturing enables fabrication of complex geometries without the cost and loss of material associated with subtractive manufacturing methods, such as machining into a final net shape. Avoiding material loss is important for magnets containing rare earth metals. Generally, recyclability and material cost drive permanent magnet motor costs. [0074] Magnet material cost constitutes up to 70% of the total cost of an electric motor and is a limiting factor to wide-scale adoption of electric vehicles. Magnet costs are significantly improved by using additive manufacturing to create a near-net-shape product, thereby incurring minimal material waste upon fabrication. [0075] In addition, by improving the demagnetization resistance of magnetic architectures through tailored crystallographic textures, the mass and volume efficiency of magnets may be increased, thereby reducing the amount of material required for matching performance efficiency of a motor or other magnet application. This benefit, in combination with the ability to produce optimized magnet shapes to optimize field utility, may improve magnet motor efficiencies in addition to decreasing the overall cost to manufacture.

[0076] Some variations provide a method of making a magnet with tailored magnetism, the method comprising:

(a) providing a feedstock composition containing one or more magnetic or magnetically susceptible materials;

(b) exposing a first amount of the feedstock composition to an energy source for melting in a scan direction, thereby generating a first melt layer;

(c) solidifying the first melt layer in the presence of an externally applied magnetic field, thereby generating a magnetic metal layer containing a plurality of individual voxels;

(d) optionally repeating steps (b) and (c) a plurality of times to generate a plurality of solid layers by sequentially solidifying a plurality of melt layers in a build direction, thereby generating a plurality of magnetic metal layers; and

(e) recovering a magnet comprising the magnetic metal layer, wherein the externally applied magnetic field has a magnetic-field orientation, defined with respect to the scan direction, that is selected to control (i) a magnetic axis within the magnetic metal layer and/or (ii) a crystallographic texture within the magnetic metal layer.

[0077] The magnetic or magnetically susceptible material in the feedstock composition may include elemental metals, metal alloys, ceramics, metal matrix composites, or combinations thereof, for example. The feedstock composition may be in the form of a powder, a wire, or a combination thereof, for example. [0078] The magnetic or magnetically susceptible material may be selected from the group consisting of Fe, Co, Ni, Cu, Cr, Mg, Mn, Zn, Sr, Ce, Si, B, C, Ba, Tb, Pr, Sm, Nd, Dy, Gd (gadolinium), and combinations or alloys thereof. Exemplary alloys that are magnetic or magnetically susceptible include, but are not limited to, Fe ₂ O ₃ , FeSi, FeNi, FeZn, MnZn, NdFeB, NdDyFeB, FeCoCr, FeAlNiCo, AlNiCo, SmCo, Dy ₂ O ₃ , SrRuCh, and combinations thereof.

[0079] A magnetically susceptible material is a material that will become magnetized in an applied magnetic field. Magnetic susceptibility indicates whether a material is attracted into or repelled out of a magnetic field. Paramagnetic materials align with the applied field and are attracted to regions of greater magnetic field. Diamagnetic materials are anti-aligned and are pushed toward regions of lower magnetic fields. On top of the applied field, the magnetization of the material adds its own magnetic field. The magnetizability of materials arises from the atomic-level magnetic properties of the particles of which they are made, typically being dominated by the magnetic moments of electrons.

[0080] The “magnetic axis” is the straight line joining two poles of a magnetized body. The torque exerted on the magnet by a magnetic field in the direction of the magnetic axis equals 0. The “crystallographic texture” is the distribution of crystallographic orientations of a polycrystalline material. A “crystallographic orientation” is defined by the plane (Miller) indices of the lattice plane of a crystal.

[0081] In some embodiments, the magnetic-field orientation is selected to control the crystallographic texture but not necessarily the magnetic axis within the magnetic metal layer. In some embodiments, the magnetic-field orientation is selected to control the magnetic axis but not necessarily the crystallographic texture within the magnetic metal layer. In preferred embodiments, the magnetic-field orientation is selected to control both the crystallographic texture as well as the magnetic axis within the magnetic metal layer.

[0082] The energy source may be a laser beam, an electron beam, or both a laser beam and an electron beam. The energy source preferably imposes a thermal gradient that melts a portion of the feedstock composition in a scan direction, rather than bulk melting the entire feedstock composition. In some embodiments, steps (b) and (c) utilize a technique selected from the group consisting of selective laser melting, electron beam melting, laser engineered net shaping, selective laser sintering, direct metal laser sintering, integrated laser melting with machining, laser powder injection, laser consolidation, direct metal deposition, directed energy deposition, plasma arc-based fabrication, ultrasonic consolidation, electric arc melting, and combinations thereof.

[0083] In some embodiments, step (b) is also conducted in the presence of the externally applied magnetic field, along with step (c). Optionally, the magnetic-field orientation may be adjusted during step (b).

[0084] Steps (b) and (c) together may be referred to as additive manufacturing or welding. When step (d) is employed to generate a plurality of solid layers by sequentially solidifying a plurality of melt layers in a build direction, then steps (b) and (c) together are typically referred to as additive manufacturing or 3D printing.

[0085] In some preferred embodiments, the magnetic-field orientation is adjusted during step (c), i.e. during solidification of the first melt layer. For example, after some voxels have been formed in a first melt layer, the magnetic-field orientation may be adjusted, after which more voxels are formed in the first melt layer.

[0086] A “voxel” is a volumetric (3D) pixel. A plurality of voxels forms a single layer having a thickness defined by the voxel height. In some embodiments, the individual voxels are defined by a characteristic voxel length scale selected from about 50 microns to about 1000 microns. In certain embodiments, the characteristic voxel length scale is selected from about 100 microns to about 500 microns. An exemplary voxel is on the order of 100 pm * 100 pm * 100 pm. Another exemplary voxel is on the order of 10 pm x 10 pm x 10 pm.

[0087] A voxel may be cubic in geometry, but that is not necessary. For example, a voxel may be rectangular or may have an irregular shape. For an arbitrary voxel geometry, there is a characteristic voxel length scale that is equivalent to the cube root of the average voxel volume. The characteristic voxel length scale may be about, at least about, or at most about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 40, 50, 75, 100, 125, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or 1000 microns, including all intervening ranges (e.g., 100-500 microns). The characteristic voxel length scale is typically a function of the laser or electron beam intensity, beam diameter, scan speed, and properties (e.g., kinematic viscosity) of the material being fabricated.

[0088] In preferred embodiments, such as in additive manufacturing, there is solidification of individual voxels and the magnetic field may be varied voxel-by- voxel, if desired. Using a highly localized energy source, and potentially using different compositions during fabrication, small voxels of a structure can be created with specific crystal orientations and magnetic properties, independently of other voxels.

[0089] Depending on the intensity of the energy delivered, each voxel may be created by melting and solidification of a starting feedstock or by sintering or other heat treatment of a region of material, for example. During solidification, a molten form of a voxel produces one or more solid grains with individual crystal structures. In some embodiments, solidified voxels contain single grains. In other embodiments, solidified voxels contain a plurality of grains having some distribution of crystallographic orientations and magnetic orientations. Geometrically, an individual voxel may be the same size as an individual grain, or may be larger than an average grain size within a magnetic metal layer. In various embodiments, an average voxel contains about, at least about, or at most about 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 50, 75, or 100 grains, including all intervening ranges.

[0090] When a voxel contains a plurality of grains each having its own crystallographic orientation and magnetic easy axis, the voxel will have a voxelaverage crystallographic orientation and a voxel-average magnetic easy axis. In some embodiments, a voxel is configured such that all grains have the same or similar crystallographic orientations and/or magnetic easy axes. In other embodiments, a voxel is configured such that individual grains have different crystallographic orientations and/or magnetic easy axes.

[0091] A magnetic metal layer (such as from additive manufacturing or welding) has crystallographic texture arising from individual grains which, in turn, form voxels. There is a magnetic easy axis for each grain, an average magnetic easy axis for each voxel, and an average magnetic easy axis for the magnetic metal layer. Using the principles of this disclosure, there may be varying degrees of alignment between these hierarchical magnetic easy axes.

[0092] In certain embodiments, a voxel contains a plurality of grains with a narrow crystallographic orientation distribution along the easy axis of the crystal as well as co-aligned magnetic domains contained within each grain. This co-alignment produces the maximum total remanent magnetic flux for the voxel. In a larger structure with a plurality of voxels, there may be a narrow crystallographic orientation distribution along the easy axis as well as co-aligned magnetic domains contained within each voxel. This co-alignment produces the maximum total remanent magnetic flux for the structure.

[0093] The grain sizes may vary widely, such as from about 0.1 microns to about 1000 microns. In various embodiments, the average grain size (within a given voxel or within the overall structure) may be about, at least about, or at most about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 75, 100, 125, 150, 200, 250, 300, 350, 400, 500, 600, 700, 800, 900, or 1000 microns.

[0094] Grain sizes may be measured by a variety of techniques, including dynamic light scattering, laser diffraction, or image analysis, for example. Dynamic light scattering is a non-invasive, well-established technique for measuring the size and size distribution of particles typically in the submicron region, and with the latest technology down to 1 nanometer. Laser diffraction is a widely used particle-sizing technique for materials ranging from hundreds of nanometers up to several millimeters in size. Exemplary dynamic light scattering instruments and laser diffraction instruments for measuring particle sizes are available from Malvern Instruments Ltd., Worcestershire, UK. Image analysis to estimate grain sizes and distributions can be done directly on photomicrographs, scanning electron micrographs, or other images.

[0095] In some embodiments, the magnetic-field orientation is selected to control voxel-specific magnetic axes within the plurality of individual voxels contained within the magnetic metal layer. In these or other embodiments, the magnetic-field orientation is selected to control voxel-specific crystallographic textures within the plurality of individual voxels contained within the magnetic metal layer.

[0096] When step (d) is conducted, to generate a plurality of solid layers by sequentially solidifying a plurality of melt layers in a build direction, the magnetic- field orientation may be adjusted in the build direction. In other words, the magnetic- field orientation may be different for one layer versus another layer, in addition to variations of the magnetic-field orientation within a layer (voxel-specific magnetic- field orientations).

[0097] The atomic structure of a crystal introduces preferential directions for magnetization. This is referred to as magnetocrystalline anisotropy. A “magnetic easy axis” is a direction inside a crystal, along which a small applied magnetic field is sufficient to reach the saturation magnetization. There can be a single easy axis or multiple easy axes. A “magnetic hard axis” is a direction inside a crystal, along which a large applied magnetic field is needed to reach the saturation magnetization. There will be a magnetic easy axis and a magnetic hard axis whether or not a magnetic field is actually being applied. The magnetic easy axis is different from the magnetic axis. A magnetic axis is only present when a magnetic field is actually applied, whereas a magnetic easy axis is a fixed property of a given crystalline material.

[0098] In some embodiments of the invention, the magnetic-field orientation may be selected to control voxel-specific magnetic easy axes within the plurality of individual voxels contained within the magnetic metal layer.

[0099] In some embodiments, the individual voxels are substantially magnetically aligned with each other, in reference to the magnetic easy axes of each voxel within a given magnetic metal layer. By “substantially magnetically aligned” is it meant that there is a standard deviation that is less than 25°, less than 20°, less than 10°, or less than 5°, calculated based on all of the magnetic easy axes within the magnetic metal layer. In certain embodiments, all magnetic easy axes are substantially aligned, such that the standard deviation is less than 2°, less than 1°, less than 0.5°, less than 0.1°, or about 0°. Remanence measurements may be used to determine the alignment of magnetic easy axes. See McCurrie, “Determination of the degree of easy axis alignment in uniaxial permanent magnets from remanence measurements” Journal of Applied Physics 52, 7344 (1981), which is hereby incorporated by reference.

[00100] In some preferred embodiments, the magnetic-field orientation is selected to control voxel-specific magnetic axes as well as voxel-specific magnetic easy axes within the plurality of individual voxels contained within the magnetic metal layer, wherein the voxel-specific magnetic axes are substantially aligned with the voxel-specific magnetic easy axes for at least a portion of the magnetic metal layer. In certain embodiments, the voxel-specific magnetic axes are substantially aligned with the voxel-specific magnetic easy axes for all of the magnetic metal layer.

[00101] In other embodiments, the magnetic-field orientation is selected to control voxel-specific magnetic axes as well as voxel-specific magnetic easy axes within the plurality of individual voxels contained within the magnetic metal layer, wherein the voxel-specific magnetic axes are configured to be at angles with the voxel-specific magnetic easy axes for at least a portion of the magnetic metal layer. [00102] In some methods, conditions in step (b) and/or step (c) are controlled such that thermal gradients assist in generating the crystallographic texture within the magnetic metal layer.

[00103] In some embodiments, different feedstock compositions, each comprising one or more magnetic or magnetically susceptible materials, are exposed to the energy source. The crystallographic texture may be adjusted during the method by performing step (b), step (c), and optionally step (d) at different times using different feedstock compositions. Different feedstock compositions may be not only different species, but also different concentrations of the same species.

[00104] Different feedstock compositions also enable the fabrication of graded compositions. For instance, the concentration of magnetic rare earth elements may be adjusted throughout a magnetic structure. One example employs local doping of Dy, Nd, or Yb in areas that are susceptible to demagnetization. Local doping may be achieved via spray additive processes, for example.

[00105] Some embodiments optimize the crystallographic texture site- specifically throughout the volume of the magnet. In contrast to conventionally processed magnetic materials with a single easy axis orientation, or a narrow distribution of easy axis orientations, texture-controlled magnets disclosed herein may possess easy axis orientations tailored to resist demagnetizing fields in regions of high susceptibility of demagnetization. Such regions may exist where demagnetizing field concentration is high and/or where orientations with respect to the magnetic field direction change rapidly, such as at corners.

[00106] Interfaces between domains are susceptible to domain reversal (demagnetization) due to a relatively low barrier to nucleation. Optimal easy axis orientations with respect to the external magnetic field preferably increase the energy barrier to nucleation of a reverse magnetic domain, thereby preserving magnetization. For example, by matching a single magnetic domain with a single grain, the resistance to domain reversal within that grain is minimized, raising the energy barrier to nucleation of a reverse domain.

[00107] The magnetic metal layer may be characterized by a microstructure with equiaxed grains. In some embodiments, the magnetic metal layer is characterized by a crack-free microstructure.

[00108] The present invention will now be further described, including with reference to the accompanying drawings that are not intended to limit the scope of the invention. The drawings are not necessarily to scale.

[00109] FIG. 1 depicts a conventional isotropic magnet (left side) and a conventional anisotropic magnet (right side). In a conventional die-pressed isotropic magnet, crystallographic orientation of grains is non-uniform and random, and magnetic alignment is along the same direction throughout the volume of the magnet. In a conventional die-pressed anisotropic magnet, magnetic alignment is along the same direction throughout the volume of the magnet, and there is some alignment and uniformity of crystallographic orientation of grains. The anisotropic variant generates a higher-energy product due to the alignment along the easy axis.

[00110] In contrast, FIG. 2 depicts a magnet with a magnetic field applied in three different directions within the three regions shown. The crystallographic orientation has not been controlled and is therefore not shown. In the magnet structure of FIG. 2, there is location-specified magnetization orientation (but not location-specified crystallographic texture), in reference to the easy axis orientation, throughout the total volume. The magnetic orientation changes by 90° across each region from left to right in FIG. 2. Because the crystallographic orientation has not been controlled, it is statistically unlikely to be aligned with the magnetic orientation. That is, in FIG. 2, a region-average magnetic axis and a region-average easy axis form a region-average alignment angle 0 that may have a high 0 standard deviation (such as 30° or higher) based on alignment-angle variance within the plurality of magnetic domains.

[00111] FIG. 3 depicts a magnet with a magnetic field in three different directions in the three regions shown. Additionally, the crystallographic orientation has been controlled through thermal gradients in solidification (e.g., from additive manufacturing or welding). In the magnet structure of FIG. 3, there is location- specified magnetization orientation and crystallographic texture, in reference to the easy axis orientation, throughout the total volume. The magnetic orientation changes by 90° from the first (left) regions to the second (middle) region, and then changes by 180° from the second to the third (right) region in FIG. 3. The crystallographic easy axis changes by approximately 90° across each regions from left to right in FIG. 3. In the first two regions, the easy axis is closely aligned with the magnetic orientation, resulting in increased energy product.

[00112] In each of FIG. 2 and FIG. 3, the height of the bulk magnet may be on the order of 1 cm, while the individual grain size may be on the order of 1 to 5 microns, for example. Thus the squares depicting multiple grains and orientations represent a small portion of the volume of each region.

[00113] The difference between the structures in FIGS. 2 and 3 is that in FIG. 2, magnetic orientation is controlled but the crystallographic orientation is not controlled, while in FIG. 3, both of the magnetic orientation and the crystallographic orientation are controlled. In either case, the magnetization orientation may be designed with specific orientations in different regions (e.g., voxels) of the magnetic structure. Magnetic domains may be larger than crystal grains. In certain preferred embodiments, each individual grain is individually tailorable, as noted in FIG. 3 (magnetic domains = crystal grains).

[00114] Some preferred variations of the invention will now be further described in reference to additive manufacturing. It will be understood that the invention is not limited to additive manufacturing, but additive manufacturing is especially able to take advantage of many principles taught herein. [00115] Additive manufacturing provides control of crystallographic orientation during 3D printing. The resultant crystallographic orientation of a grain is dependent on several contributing thermodynamic driving forces. One such factor is the direction of the maximum thermal gradient, in which solidifying cubic crystals tend to preferentially grow with a <100> orientation. The thermal gradient can be controlled using a laser scan strategy by locally heating with a variety of spatially and/or temporally varying patterns. The formation of crystallographic texture can also be tailored during solidification and subsequent solid-state transformations through the application of an external magnetic field, potentially producing more texture uniformity with specified locality and direction.

[00116] In some embodiments, the magnetic performance is improved by controlling crystallographic orientation (texture) of the grains in addition to the magnetization orientation in the microstructure. This control is especially powerful when crystallographic texture and magnetic orientation are both tailored in a synergistic way during additive manufacturing. To this end, the grains may be crystallographically oriented in the (or a) direction that allows the highest remanent magnetization; simultaneously, a magnetic field may be applied to orient the magnetization in that same direction. The result is a magnet with optimal crystallographic and magnetic orientation and therefore the maximum energy product. Magnetic materials may also be optimized by 3D tailoring of crystallographic texture in regions susceptible to demagnetization. By employing additive manufacturing, local thermal, magnetic, and stress fields may be manipulated in the production of magnetic materials having selected crystallographic texture(s) with location specificity.

[00117] Some variations of the invention provide a method of making a magnet with tailored magnetism by additive manufacturing, the method comprising:

(a) providing a feedstock composition containing base particles and one or more surface-modifying particles that are chemically and/or physically disposed on surfaces of the base particles, wherein the surface-modifying particles are magnetic or magnetically susceptible;

(b) exposing a first amount of the feedstock composition to an energy source for melting in a scan direction, thereby generating a first melt layer; (c) solidifying the first melt layer in the presence of an externally applied magnetic field, thereby generating a magnetic metal layer containing a plurality of individual voxels;

(d) optionally repeating steps (b) and (c) a plurality of times to generate a plurality of solid layers by sequentially solidifying a plurality of melt layers in a build direction, thereby generating a plurality of magnetic metal layers; and

(e) recovering a magnet comprising the magnetic metal layer, wherein the externally applied magnetic field has a magnetic-field orientation, defined with respect to the scan direction, that is selected to control a magnetic axis within the magnetic metal layer.

[00118] In some embodiments, the energy source is a laser beam, an electron beam, or a combination thereof. Steps (b) and (c) may utilize a technique selected from the group consisting of selective laser melting, electron beam melting, laser engineered net shaping, selective laser sintering, direct metal laser sintering, integrated laser melting with machining, laser powder injection, laser consolidation, direct metal deposition, directed energy deposition, plasma arc-based fabrication, ultrasonic consolidation, electric arc melting, and combinations thereof, for example. [00119] The magnetic-field orientation may be adjusted during step (c). For example, the magnetic-field orientation may be adjusted or selected to control a crystallographic texture within the magnetic metal layer.

[00120] In some methods, step (b) is also conducted in the presence of the externally applied magnetic field, along with step (c). Optionally, the magnetic-field orientation may be adjusted during step (b).

[00121] In some embodiments, during step (c), the surface-modifying particles are substantially magnetically aligned with each other. In these or other embodiments, during step (c), the surface-modifying particles nucleate growth of grains that are magnetically aligned with each other.

[00122] When step (d) is conducted, the magnetic-field orientation may be adjusted in the build direction. The magnetic-field orientation may be adjusted at every build layer, or may switch back and forth between two different orientations for successive layers, or may incrementally change angle as the build proceeds, as just a few examples of build strategies. [00123] FIG. 4 is a schematic set-up 400 of additive manufacturing in the absence of a magnetic field. A surface-functionalized powder 410 forms a powder bed. The surface-functionalized powder 410 contains powder particles 411 with smaller particles 412 attached to surfaces of the powder particles 411. The scale bar (20 pm) for a powder particle is exemplary only. During selective laser melting or electron beam melting, a laser or electron beam 420 (not to scale) melts the surface- functionalized powder 410, creating a wave which can sweep it in. Marangoni effects from high thermal gradients, along with laser-induced recoil pressure, induce a turbulent mixing state in the liquid melt pool 430. Particulates then nucleate grains in the undercooled region 440, resulting in a solidified and equiaxed grain structure 450. In FIG. 4, the scan direction is perpendicular to the laser or electron beam 420, and the build direction is parallel to the laser or electron beam 420.

[00124] FIG. 4 depicts two electromagnets 460 that are not magnetically active (electrical current is off). An electromagnet 460 is made from a coil of wire that acts as a magnet when an electric current passes through the coil. The coil may be wrapped around a core of soft ferromagnetic material such as mild steel, to enhance the magnetic field produced by the coil. The energized coil creates a magnetic field. When the current is shut off, the magnetic field disappears.

[00125] FIG. 5 is the same additive-manufacturing set-up as in FIG. 4, except that the electromagnets 460 are magnetically active (electrical current is on), creating an applied magnetic field. Magnetic field lines are depicted in FIG. 5 as curved arrows from the left-hand electromagnet to the right-hand electromagnet.

[00126] FIG. 6 is the same additive-manufacturing set-up as in FIG. 4, except that the electromagnets 460 are magnetically active (electrical current is on) and are disposed at an angled orientation, creating an applied magnetic field that is at an angle with respect to the additive-manufacturing build layer. The angle may be adjusted for each build layer, if desired.

[00127] The base particles may be metals, metal alloys, ceramics, carbon, polymers, or combinations thereof, for example, and are not necessarily magnetic or magnetically susceptible. In certain embodiments, the base particles are magnetic or magnetically susceptible. [00128] In some embodiments, the surface-modifying particles are ferromagnetic. In these or other embodiments, the surface-modifying particles nucleate growth of grains that are ferromagnetic.

[00129] The magnetic or magnetically susceptible material (within the surfacemodifying particles) may be selected from the group consisting of Fe, Co, Ni, Cu, Cr, Mg, Mn, Zn, Sr, Ce, Si, B, C, Ba, Tb, Pr, Sm, Nd, Dy, Gd, and combinations or alloys thereof. Exemplary alloys that are magnetic or magnetically susceptible include, but are not limited to, Fe2O3, FeSi, FeNi, FeZn, MnZn, NdFeB, NdDyFeB, FeCoCr, FeAlNiCo, AlNiCo, SmCo, Dy2Ch, SrRuCh, and combinations thereof.

[00130] In some embodiments, without limitation, an additive-manufacturing feedstock is a powder that is surface-functionalized with a plurality of nanoparticles. The nanoparticles may promote heterogeneous nucleation in the melt pool to induce equiaxed grain growth. In some embodiments, the nanoparticles are magnetic or magnetically susceptible and become magnetically aligned during solidification to produce a crystallographic texture dictated by an external magnetic field.

Alternatively, or additionally, the nanoparticles — whether or not they are magnetic or magnetically susceptible — may induce growth of a magnetic phase which could then be magnetically aligned with the magnetic-field direction.

[00131] The principles of this invention are alloy-agnostic and can be applied to any powder-based additive manufacturing process as well as additive manufacturing processes employing other precursor geometries, such as (but not limited to) wires.

[00132] Generally speaking, the base particles and/or the surface-modifying particles may be selected from the group consisting of Al, Si, Fe, Cu, Ni, Mn, Mg, Cr, Zn, V, Ti, Bi, Ga, Pb, Zr, H, Li, Be, B, C, N, O, F, Na, P, S, Cl, K, Ca, Sc, Co, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Te, I, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Ce, Nd, and combinations thereof, for example.

[00133] In general, the geometry of the feedstock composition is not limited and may be, for example, in the form of powder particles, wires, rods, bars, plates, films, coils, spheres, cubes, prisms, cones, irregular shapes, or combinations thereof. In certain embodiments, the feedstock composition is in the form of a powder, a wire, or a combination thereof (e.g., a wire with powder on the surface). When the feedstock composition is in the form of powder, the powder particles may have an average diameter from about 1 micron to about 500 microns, such as about 10 microns to about 100 microns, for example. When the feedstock composition is in the form of a wire, the wire may have an average diameter from about 10 microns to about 1000 microns, such as about 50 microns to about 500 microns, for example. [00134] The energy source for additive manufacturing may be provided by a laser beam, an electron beam, alternating current, direct current, plasma energy, induction heating from an applied magnetic field, ultrasonic energy, other sources, or a combination thereof. Typically, the energy source is a laser beam or an electron beam.

[00135] Process steps (b) and (c) may utilize a technique selected from the group consisting of selective laser melting, electron beam melting, laser engineered net shaping, selective laser sintering, direct metal laser sintering, integrated laser melting with machining, laser powder injection, laser consolidation, direct metal deposition, wire-directed energy deposition, plasma arc-based fabrication, ultrasonic consolidation, and combinations thereof, for example.

[00136] In certain embodiments, the additive manufacturing process is selected from the group consisting of selective laser melting, energy-beam melting, laser engineered net shaping, and combinations thereof.

[00137] Selective laser melting utilizes a laser (e.g., Yb-fiber laser) to provide energy for melting. Selective laser melting is designed to use a high power-density laser to melt and fuse metallic powders together. The process has the ability to fully melt the metal material into a solid 3D part. A combination of direct drive motors and mirrors, rather than fixed optical lens, may be employed. An inert atmosphere is usually employed. A vacuum chamber can be fully purged between build cycles, allowing for lower oxygen concentrations and reduced gas leakage. Selective laser melting is a type of powder bed-based additive manufacturing.

[00138] Electron beam melting uses a heated powder bed of metal that is then melted and formed layer by layer, in a vacuum, using an electron beam energy source similar to that of an electron microscope. Metal powder is welded together, layer by layer, under vacuum. Electron beam melting is another type of powder bed-based additive manufacturing. [00139] Laser engineering net shaping is a powder-injected technique operates by injecting metal powder into a molten pool of metal using a laser as the energy source. Laser engineered net shaping is useful for fabricating metal parts directly from a computer-aided design solid model by using a metal powder injected into a molten pool created by a focused, high-powered laser beam. Laser engineered net shaping is similar to selective laser sintering, but the metal powder is applied only where material is being added to the part at that moment. Note that “net shaping” is meant to encompass “near net” fabrication.

[00140] Direct metal laser sintering process works by melting fine powders of metal in a powder bed, layer by layer. A laser supplies the necessary energy and the system operates in a protective atmosphere, typically of nitrogen or argon.

[00141] Another approach utilizes powder injection to provide the material to be deposited. Instead of a bed of powder that is reacted with an energy beam, powder is injected through a nozzle that is then melted to deposit material. The powder may be injected through an inert carrier gas or by gravity feed. A separate shielding gas may be used to protect the molten metal pool from oxidation.

[00142] Directed energy deposition utilizes focused energy (either an electron beam or laser beam) to fuse materials by melting as the material is being deposited. Powder or wire feedstock can be utilized with this process. Powder-fed systems, such as laser metal deposition and laser engineered net shaping, blow powder through a nozzle, with the powder melted by a laser beam on the surface of the part. Laserbased wirefeed systems, such as laser metal deposition-wire, feed wire through a nozzle with the wire melted by a laser, with inert gas shielding in either an open environment (gas surrounding the laser), or in a sealed gas enclosure or chamber.

[00143] Powder bed-based additive manufacturing is preferred for its ability to produce near-net-shape products as well as the smaller tailorable voxel size (such as about 200 pm or less) compared to directed energy deposition (conventionally >500 pm).

[00144] Some embodiments utilize wire feedstock and an electron beam heat source to produce a near-net shape part inside a vacuum chamber. An electron beam gun deposits metal via the wire feedstock, layer by layer, until the part reaches the desired shape. Then the part optionally undergoes finish heat treatment and machining. Wire can be preferred over powder for safety and cost reasons.

[00145] Additive manufacturing provides the opportunity to tailor local structure voxel-by-voxel in a serial, layered process. A processed voxel is the volume affected by heat input from the direct energy source in a layer-based approach, which volume includes the melt pool as well as the surrounding heat-affected zone. The solidification crystallographic texture may be controlled by the direction of heat extraction. In addition to the thermal field, a magnetic field may be applied during processing to control both crystallographic texture and magnetization orientation.

The external magnetic field may be generated by means of an induction coil, multiple induction coils, a permanent magnet, or an array of permanent magnets, for example. [00146] In some embodiments, the additively manufactured magnet has a microstructure with a crystallographic texture that is not solely oriented in the additive-manufacturing build direction. For example, the solid layers may have differing primary growth-direction angles with respect to each other.

[00147] The method is not limited in principle to the number of solid layers that may be fabricated. A “plurality of solid layers” in step (d) means at least 2 layers, such as at least 10 individual solid layers. The number of solid layers may be much greater than 10, such as about 100, 1000, or more. As noted earlier, in the case of welding or single-layer manufacturing, there may be a single layer in the final structure. Multiple-layer welding is another embodiment.

[00148] The plurality of solid layers may be characterized by an average layer thickness of at least 10 microns, such as about 10, 20, 30, 40, 50, 75, 100, 150, or 200 microns, for example.

[00149] Each solid layer may contain a number of voxels. In a special case for a substantially vertical build (e.g., a narrow column), there may be a single voxel per layer. The average number of voxels per layer may be about, at least about, or at most about 2, 3, 4, 5, 10, 20, 30, 40, 50, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, or 1000, including all intervening ranges, for example.

[00150] One or more solid layers may have a microstructure with equiaxed grains. A microstructure that has “equiaxed grains” means that at least 90 vol%, preferably at least 95 vol%, and more preferably at least 99 vol% of the metal alloy contains grains that are roughly equal in length, width, and height. In some embodiments, at least 99 vol% of the magnet contains grains that are characterized in that there is less than 25%, preferably less than 10%, and more preferably less than 5% standard deviation in each of average grain length, average grain width, and average grain height. Equiaxed grains may result when there are many nucleation sites arising from grain-refining nanoparticles contained in the microstructure. [00151] The surface-modifying particles of some embodiments are grainrefining nanoparticles. The grain-refining nanoparticles are preferably present in a concentration of at least 0.01 vol%, such as at least 0.1 vol%, at least 1 vol%, or at least 5 vol% of the feedstock composition. In various embodiments, the grainrefining nanoparticles are present in a concentration of about, or at least about, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 vol%.

[00152] In some embodiments, the grain-refining nanoparticles are lattice- matched to within ±5% compared to an otherwise-equivalent material containing the base particles but not the grain-refining nanoparticles. In certain embodiments, the grain-refining nanoparticles are lattice-matched to within ±2% or within ±0.5% compared to a material containing the base particles but not the grain-refining nanoparticles.

[00153] Preferably, the microstructure of the additively manufactured magnet is substantially crack-free. The avoidance of cracks can be important for magnets. For example, samarium-cobalt magnets are brittle and prone to cracking and chipping. Crack-free SmCo-based permanent or soft magnets may be fabricated. [00154] A magnet microstructure that is “substantially crack-free” means that at least 99.9 vol% of the metal alloy contains no linear or tortuous cracks that are greater than 0.1 microns in width and greater than 10 microns in length. In other words, to be considered a crack, a defect must be a void space that is at least 0.1 microns in width as well as at least 10 microns in length. A void space that has a length shorter than 10 microns but larger than 1 micron, regardless of width, can be considered a porous void (see below). A void space that has a length of at least 10 microns but a width shorter than 0.1 microns is a molecular-level gap that is not considered a defect. [00155] Typically, a crack contains open space, which may be vacuum or may contain a gas such as air, CO2, N2, and/or Ar. A crack may also contain solid material different from the primary material phase of the metal alloy. The non-desirable material disposed within the crack may itself contain a higher porosity than the bulk material, may contain a different crystalline (or amorphous) phase of solid, or may be a different material altogether, arising from impurities during fabrication, for example.

[00156] The magnet microstructure may be substantially free of porous defects, in addition to being substantially crack-free. “Substantially free of porous defects” means at least 99 vol% of the magnet contains no porous voids having an effective diameter of at least 1 micron.

[00157] Preferably, at least 80 vol%, more preferably at least 90 vol%, even more preferably at least 95 vol%, and most preferably at least 99 vol% of the magnet contains no porous voids having an effective diameter of at least 1 micron. A porous void that has an effective diameter less than 1 micron is not typically considered a defect, as it is generally difficult to detect by conventional non-destructive evaluation. Also preferably, at least 90 vol%, more preferably at least 95 vol%, even more preferably at least 99 vol%, and most preferably at least 99.9 vol% of the metal alloy contains no larger porous voids having an effective diameter of at least 5 microns.

[00158] Typically, a porous void contains open space, which may be vacuum or may contain a gas such as air, CO2, N2, and/or Ar. Porous voids may be reduced or eliminated, in some embodiments. For example, additively manufactured metal parts may be hot-isostatic-pressed to reduce residual porosity, and optionally to arrive at a final additively manufactured magnet that is substantially free of porous defects in addition to being substantially crack-free.

[00159] In some preferred embodiments, a starting feedstock is surface- functionalized. “Surface-functionalized” and “surface functionalization” refer to a surface modification on feedstock materials, which modification affects the solidification behavior such as solidification rate, yield, grain quality, heat release, etc. In various embodiments, a feedstock is functionalized with about 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80%, 85%, 90%, 95%, 99%, or 100% of the surface area having surface-functionalization modifications. The surface modification may be a surface-chemistry modification, a physical surface modification, or a combination thereof.

[00160] In some embodiments, the surface functionalization includes a nanoparticle coating and/or a microparticle coating. The nanoparticles and/or microparticles may include a metal, ceramic, polymer, or carbon, or a composite or combination thereof. The surface functionalization preferably includes nanoparticles and/or microparticles that are chemically or physically disposed on the surface of the powder materials. Nanoparticles and/or microparticles are the surface-modifying particles in step (a).

[00161] Nanoparticles are particles with the largest dimension between about 1 nm and about 5000 nm. A preferred size of nanoparticles is about 2000 nm or less, about 1500 nm or less, or about 1000 nm or less. In some embodiments, nanoparticles are at least 50 nm in size. In various embodiments, the average nanoparticle size is about 2, 5, 10, 25, 50, 100, 200, 300, 400, 500, 1000, 2000, 3000, 4000, or 5000 nanometers. Microparticles are particles with the largest dimension between about 1 micron and 1000 microns. The nanoparticle or microparticle size may be selected based on the desired properties and function of the final magnet.

[00162] Nanoparticles or microparticles may be spherical or of arbitrary shape with the largest dimension typically not exceeding the above largest dimensions. The nanoparticles or microparticles may include a coating of one or more layers of a different material. Mixtures of nanoparticles and microparticles may be used. In some embodiments, microparticles themselves are coated with nanoparticles, and the microparticle/nanoparticle composite is incorporated as a coating or layer on base particles.

[00163] The number of nanoparticles per microparticle can vary widely. The average number of individual nanoparticles disposed on one microparticle (equivalently, the average number ratio of nanoparticles to powder microparticles) may be about 10, about 10 ² , about 10 ³ , about 10 ⁴ , about 10 ⁵ , or about 10 ⁶ , for example. The nanoparticle distribution on a feedstock particle surface can vary. In some embodiments, surface regions contain a relatively higher concentration of nanoparticles, which may be agglomerated at the surface in those regions. [00164] The nanoparticle surface coverage may also vary widely, from about 1% to 100%, in various embodiments. The nanoparticle surface coverage is the average area fraction of feedstock particles that is covered by assembled nanoparticles. For example, the nanoparticle surface coverage may be about, or at least about, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%. Due to the small size of nanoparticles, benefits are possible with less than 1% surface area coverage.

[00165] In some embodiments, at least 1% of the surface area of the microparticles contains nanoparticles that are chemically and/or physically disposed on the microparticle surfaces. When higher nanoparticle concentrations are desired in the final material, it is preferred that a higher surface area of the microparticles contains nanoparticles. In various embodiments, at least 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% of the total surface area of the microparticles contains nanoparticles that are chemically and/or physically disposed on the microparticle surfaces.

[00166] In some embodiments, the microparticles have an average microparticle size from about 1 micron to about 1 centimeter. In various embodiments, the average microparticle size is about 5 microns, 10 microns, 50 microns, 100 microns, 200 microns, 500 microns, 1 millimeter, 5 millimeters, or 10 millimeters.

[00167] The nanoparticles or microparticles are typically a different composition than the base particles. Nanoparticles or microparticles may include metals, hydrides, carbides, nitrides, borides, oxides, intermetallics, or other materials which upon processing form one or more of the aforementioned materials.

[00168] In some embodiments, surface functionalization is in the form of a continuous coating or an intermittent coating. A continuous coating covers at least 90% of the surface, such as about 95%, 99%, or 100% of the surface (recognizing there may be defects, voids, or impurities at the surface). An intermittent coating is non-continuous and covers less than 90%, such as about 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, 5%, 2%, 1%, or less of the surface. An intermittent coating may be uniform (e.g., having a certain repeating pattern on the surface) or non-uniform (e.g., random). [00169] In general, a functionalization coating may be continuous or discontinuous. The coating may have several characteristic features. In one embodiment, the coating may be smooth and conformal to the underlying surface. In another embodiment, the coating may be nodular. The nodular growth is often characteristic of kinetic limitations of nanoparticle assembly. For example, the coating may look like cauliflower or a small fractal growing from the surface. These features can be affected by the underling materials, the method of coating, reaction conditions, etc.

[00170] A coating may or may not be in the form of nanoparticles or microparticles. That is, the coating may be derived from nanoparticles or microparticles, and discrete nanoparticles or microparticles may no longer be present. Various coating techniques may be employed, such as (but not limited to) electroless deposition, immersion deposition, or solution coating. The coating thickness is preferably less than about 20% of the underlying particle diameter, such as less than 15%, 10%, 5%, 2%, or 1% of the underlying particle diameter.

[00171] In some embodiments, the surface functionalization also includes direct chemical or physical modification of the surface of the powder materials, such as to enhance the bonding of the nanoparticles or microparticles. Direct chemical modification of the surface of the powder materials, such as addition of molecules, may also be utilized to affect the solidification behavior of the powder materials. A plurality of surface modifications described herein may be used simultaneously.

[00172] The selection of composition will be dependent on the desired magnet properties and should be considered on a case-by-case basis. Someone skilled in the art of material science or metallurgy will be able to select the appropriate materials for the intended use, based on the information provided in this disclosure.

[00173] Nanoparticles or microparticles may be attached using electrostatic forces, Van der Waals forces, chemical bonds, physical bonds, and/or any other force. A chemical bond is the force that holds atoms together in a molecule or compound. Electrostatic and Van der Waals forces are examples of physical forces that can cause bonding. A physical bond is a bond that arises when molecular entities become entangled in space. Typically, chemical bonds are stronger than physical bonds. Chemical bonds may include ionic bonds, covalent bonds, or a combination thereof. [00174] In some embodiments, the surface-modifying particles have an average particles size of 10 microns or less, such as an average particles size of 1 micron or less. The surface-modifying particles may be spherical, non-spherical (e.g., pyramidal or cubic), or random in shape.

[00175] In some embodiments, the magnetic-field orientation is selected to control voxel-specific magnetic axes within the plurality of individual voxels contained within the magnetic metal layer. In these or other embodiments, the magnetic-field orientation is selected to control voxel-specific crystallographic textures within the plurality of individual voxels contained within the magnetic metal layer. In certain embodiments, the magnetic-field orientation is selected to control voxel-specific magnetic easy axes within the plurality of individual voxels contained within the magnetic metal layer.

[00176] In some embodiments, the individual voxels are substantially magnetically aligned with each other. In some embodiments, the individual voxels are each characterized by a magnetic easy axis that is substantially aligned across the plurality of individual voxels.

[00177] In certain embodiments, the magnetic-field orientation is selected to control voxel-specific magnetic axes as well as voxel-specific magnetic easy axes within the plurality of individual voxels contained within the magnetic metal layer, wherein the voxel-specific magnetic axes are substantially aligned with the voxelspecific magnetic easy axes for at least a portion of the magnetic metal layer. The voxel-specific magnetic axes may be substantially aligned with the voxel-specific magnetic easy axes for all of the magnetic metal layer.

[00178] In other embodiments, the magnetic-field orientation is selected to control voxel-specific magnetic axes as well as voxel-specific magnetic easy axes within the plurality of individual voxels contained within the magnetic metal layer, wherein the voxel-specific magnetic axes are configured to be at angles with the voxel-specific magnetic easy axes for at least a portion of the magnetic metal layer. [00179] In some methods, conditions in step (b) and/or step (c) are controlled such that thermal gradients assist in generating the crystallographic texture within the magnetic metal layer. [00180] Optionally, different feedstock compositions, each comprising one or more magnetic or magnetically susceptible surface-modifying particles, are exposed to the energy source, and the crystallographic texture is adjusted during the method by performing step (b), step (c), and optionally step (d) at different times using the different feedstock compositions.

[00181] In certain embodiments, neither the base particles nor the surfacemodifying particles are magnetic or magnetically susceptible, but during fabrication, grains are produced which are magnetic or magnetically susceptible. An externally applied magnetic field may align those grains during solidification. Some embodiments thus provide a method of making a magnet with tailored magnetism by additive manufacturing, the method comprising:

(a) providing a feedstock composition containing base particles and one or more surface-modifying particles that are chemically and/or physically disposed on surfaces of the base particles, wherein the surface-modifying particles are not necessarily magnetic or magnetically susceptible;

(b) exposing a first amount of the feedstock composition to an energy source for melting in a scan direction, thereby generating a first melt layer;

(c) solidifying the first melt layer in the presence of an externally applied magnetic field, thereby generating a magnetic metal layer containing a plurality of individual voxels, wherein at least some of the voxels contain grains that are magnetic or magnetically susceptible;

(d) optionally repeating steps (b) and (c) a plurality of times to generate a plurality of solid layers by sequentially solidifying a plurality of melt layers in a build direction, thereby generating a plurality of magnetic metal layers; and

(e) recovering a magnet comprising the magnetic metal layer, wherein the externally applied magnetic field has a magnetic-field orientation, defined with respect to the scan direction, that is selected to control a magnetic axis within the magnetic metal layer.

[00182] In additive manufacturing, post-production processes such as heat treatment, light machining, surface finishing, coloring, stamping, or other finishing operations may be applied. Also, several additive manufactured parts may be joined together chemically or physically to produce a final magnet. [00183] In some methods, the magnet with tailored magnetism is a permanent magnet. A “permanent magnet” (or “hard magnet”) means a magnet with an intrinsic magnetic coercivity of 1000 A/m (amperes per meter) or greater. For example, a permanent magnet may be selected from the group consisting of a NdFeB magnet, a NdDyFeB magnet, a FeCoCr magnet, a FeAlNiCo magnet, a SmCo magnet, and combination thereof. In some methods, the permanent magnet is an additively manufactured permanent magnet. In some methods, the permanent magnet is a welded permanent magnet.

[00184] Soft magnetic materials are those materials that are easily magnetized and demagnetized. A “soft magnet” (or “temporary magnet”) has intrinsic magnetic coercivity less than 1000 A/m. In some methods, the magnet with tailored magnetism is a soft magnet. A soft magnet may contain a material selected from the group consisting of Fe, Co, Ni, Mg, Zn, Sr, Ba, Sm, C, Fe2Ch, FeSi, FeNi, FeZn, MnZn, and combinations thereof, for example. In some methods, the soft magnet is an additively manufactured soft magnet. In some methods, the soft magnet is a welded soft magnet.

[00185] Some variations provide a soft-magnet structure comprising: a region having a plurality of magnetic domains and a region-average magnetic axis, wherein each of the magnetic domains has a domain magnetic axis, wherein each domain magnetic axis is substantially aligned with the region-average magnetic axis, and wherein the plurality of magnetic domains is characterized by an average magnetic domain size; and within the region, a plurality of metal-containing grains, wherein the plurality of metal-containing grains is characterized by an average grain size, wherein each of the magnetic domains has a domain easy axis that is dictated by a crystallographic texture of the metal-containing grains; wherein the region has a region-average easy axis based on average value of the domain easy axis within the region; and wherein the region-average magnetic axis and the region-average easy axis form a region-average alignment angle 0 that preferably has a 0 standard deviation of less than 30° based on alignment-angle variance within the plurality of magnetic domains. [00186] In various embodiments, a magnet with tailored magnetism has an intrinsic magnetic coercivity order of magnitude of about, at least about, or at most about 0.1, 1, 10, 100, 1000, 10 ⁴ , 10 ⁵ , or 10 ⁶ A/m, including all intervening ranges. [00187] In various embodiments, a magnet with tailored magnetism has a total energy product of about, at least about, or at most about 1, 10, 50, 100, 200, 300, 400, or 500 kJ/m ³ , including all intervening ranges.

[00188] In some embodiments, a magnet with tailored magnetism has a structure with more than one tailored magnetic region. One example is a Halbach array. Halbach arrays are conventionally assembled by bonding individually uniform texture and magnetic orientation magnets in a sequence of orientations that accentuates the field on one side of the magnet at the expense of the field on the opposing side. This conformation sacrifices field uniformity due to the large size (>1 mm) of the magnets used conventional Halbach arrays. By using the disclosed voxelbased approach with resolutions below 1 mm (e.g., 50 pm beam size for a laser), a Halbach array configuration may be constructed at the micron scale, thereby enabling more-uniform, high-flux magnetic fields to be generated.

EXAMPLE

[00189] This example demonstrates crystallographic texture control of a laser- welded Nd2Fei4B magnet structure.

[00190] A Nd2Fei4B magnet structure is processed in a laser-welding machine with an external magnetic field. A DC magnetic field with flux density of approximately 1 T is applied parallel to the horizontal face of a sintered ISkhFeuB magnet structure. Single-track weld lines are generated using a pulsed infrared laserwelder moving the surface through the static DC field.

[00191] FIG. 7 shows photomicrographs of the ISkhFeuB magnet microstructure with a shifted dendrite growth direction against the direction of maximum thermal gradient. FIG. 8 shows a photomicrograph top view of the laser- welded Nd2Fei4B magnet structure. FIG. 9 shows the increase in NdFeB easy axis [001] texture along the scan vector direction in IPF (inverse pole figure) density plots. EBSD (electron backscatter diffraction) maps are provided for reference orientations. The IPF density plots are shown in the lower half of FIG. 9, and the EBSD maps are shown in the upper half of FIG. 9.

[00192] Epitaxial dendritic solidification tends to grow in the direction of the largest thermal gradient. However, under an external magnetic field, the solidification direction is unaligned with the maximum thermal gradient. Adjustment of the field direction influences texture evolution (from the dendritic solidification direction) with greater or less magnitude in accordance with the magnitude and field applied.

[00193] In this detailed description, reference has been made to multiple embodiments and to the accompanying drawings in which are shown by way of illustration specific exemplary embodiments of the invention. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, and it is to be understood that modifications to the various disclosed embodiments may be made by a skilled artisan.

[00194] Where methods and steps described above indicate certain events occurring in certain order, those of ordinary skill in the art will recognize that the ordering of certain steps may be modified and that such modifications are in accordance with the variations of the invention. Additionally, certain steps may be performed concurrently in a parallel process when possible, as well as performed sequentially.

[00195] All publications, patents, and patent applications cited in this specification are herein incorporated by reference in their entirety as if each publication, patent, or patent application were specifically and individually put forth herein.

[00196] The embodiments, variations, and figures described above should provide an indication of the utility and versatility of the present invention. Other embodiments that do not provide all of the features and advantages set forth herein may also be utilized, without departing from the spirit and scope of the present invention. Such modifications and variations are considered to be within the scope of the invention defined by the claims.