Patent Application
20180122570
The present invention relates generally to bonded permanent magnets and methods for producing them. The invention also relates to additive manufacturing methods, particularly big area additive manufacturing (BAAM).
Permanent bonded magnets are well known. Bonded permanent magnets are typically fabricated by blending magnetic powders with a polymer as binder, and then molding the blend into desired shapes utilizing several commercial processing methods including injection molding, compression molding, extrusion, and calendering. Recently, bonded permanent magnets have experienced accelerated industrial applications due to their advantages, such as ability to be produced in intricate shapes, low weight and cost, superior mechanical properties and corrosion resistance. Nd2Fe14B is a particularly well known permanent magnet used in many industrial applications. Nd2Fe14B is known to adopt a tetragonal crystal structure (P42/mnm) with the easy magnetic axis along the c axis (Herbst, J. F., et al. Phys. Rev. B. 29, 4176-4178, 1984). Nd2Fe14B possesses a magnetic energy as large as 512 kJ/m3 (64 MGOe), with a Curie temperature Tc=585 K and a high magnetic anisotropy constant K1 of 4.5 MJ/m3 arising from the strong spin-orbit coupling in Nd (Sagawa, M., et al. J. Appl. Phys. 57, 4094, 1985). Magnet powder properties, processing temperature, loading factor, magnet density and degree of orientation are critical process variables for improving magnetic and mechanical properties of NdFeB bonded magnets.
However, current methods for producing them are being significantly challenged by an increasing demand for bonded permanent magnets of various intricate shapes and sizes, and with higher mechanical and magnetic field strengths. Although some additive manufacturing methods, such as binder jetting, have been attempted for producing bonded permanent magnets, the bonded magnet often exhibits sub-standard hard magnetic properties due to limitations in producing sufficiently dense parts. Considering the above, there would be a significant advantage in a method that could produce permanent bonded magnets of any desired shape, intricacy, and size, and with higher than conventional mechanical strengths and magnetic field strengths.
The present disclosure is directed to methods for producing permanent bonded magnets of any of a variety of shapes, sizes, and intricacies, and with exceptional mechanical and magnetic field strengths. In the method, a precursor material containing a thermoplastic polymer and particles having a hard magnetic material composition is used as feedstock in a big area additive manufacturing (BAAM) system to produce a bonded permanent magnet. By virtue of the unbounded build space afforded by the BAAM system, a bonded permanent magnet of unlimited size can be produced, or alternatively, a structure of unlimited size (e.g., a motor, engine, vehicle, or industrial machine) and shape can be produced in which a component of the structure is magnetic.
In particular embodiments, the method includes: (i) incorporating components of a solid precursor material into at least one deposition head of at least one multi-axis robotic arm of a big area additive manufacturing (BAAM) system, the components of the solid precursor material comprising a thermoplastic polymer and particles having a hard magnetic material composition, wherein the thermoplastic polymer has a melting point of at least 175° C.; the deposition head performs melting, compounding, and extruding functions; and the BAAM system has an unbounded open-air build space; and (ii) depositing an extrudate of the solid precursor material from the deposition head, the extrudate being at a temperature above the glass transition temperature of the solid precursor material when exiting an orifice of the deposition head, and depositing the extrudate layer-by-layer from the deposition head until an object composed of the extrudate is formed. In the layer-by-layer deposition, the extrudate is allowed to cool after each deposition to produce the bonded permanent magnet. The method advantageously provides a bonded permanent magnet that retains the magnetic properties of the particles having a hard magnetic material composition with substantially no loss (e.g., up to or less than 5% loss) in the magnetic properties.
In the disclosed process, a material containing a thermoplastic polymer (i.e., “polymeric binder”) and particles having a hard magnetic material composition (i.e., magnetic particles) is employed as a solid precursor material (i.e., feed) in a BAAM process. As well known in the art, the BAAM process employs an unbounded open-air build space in which at least one, and typically, a multiplicity, of deposition heads controlled by one or a multiplicity of multi-axis robotic arms operate in concert to construct an object. In the BAAM process, the feed material is processed within and ultimately deposited from the deposition head layer-by-layer as an extrudate, which cools over time to produce the bonded permanent magnet. The BAAM process considered herein may use only the hard magnetic precursor material as feed for the entire BAAM process, or the BAAM process may employ the hard magnetic precursor material as feed in one or more deposition heads and may employ another (non-magnetic) feed in one or more other deposition heads to construct an object with magnetic and non-magnetic portions. As well known, the deposition head in a BAAM process is designed to combine melting, compounding, and extruding functions to produce and deposit an extrudate of the precursor material layer-by-layer. The deposition heads are moved and precisely positioned by the multi-axis robotic arm, which can be either stationary or mounted on a multi-axis or conventional three-axis gantry system. The multi-axis robotic arms are, in turn, instructed by a computer program, as generally provided by a computer-aided manufacturing (CAM) software package. As also well known, in the BAAM process, one deposition head may be partly or solely responsible for building a specific region of the overall object, but generally coordinates with at least one other deposition head, which is involved in building another region of the overall object. The BAAM process is described in detail in, for example, C. Holshouser et al., Advanced Materials & Processes, 15-17, March 2013, and M. R. Talgani et al., SAMPE Journal, 51(4), 27-36, July/August 2015, the contents of which are herein incorporated by reference in their entirety.
The thermoplastic polymer can be any polymer that can be melted, compounded, and extruded in the deposition head of a BAAM system. The thermoplastic polymer should also have the ability to harden after deposition and cooling. For purposes of the invention, the thermoplastic polymer preferably has a melting point of at least or above 175° C., 180° C., 185° C., 190° C., 195° C., 200° C., 225° C., 250° C., 275° C., or 300° C. Some examples of such thermoplastic polymers include polyamides (e.g., Nylon 6,6), polyphenylene sulfide, polyphenylene oxide, acrylonitrile butadiene styrene, polyether ether ketone, polyoxymethylene, polyether sulfone, polycarbonates, polyetherimide, polyvinyl addition polymers (e.g., polyacrylonitrile, polyvinylchloride, polytetrafluoroethylene, and polystyrene), polyesters, and polybenzimidazole. In some embodiments, the thermoplastic polymer is a homopolymer, which may have any of the above compositions. In other embodiments, the thermoplastic polymer is a copolymer, which may be, for example, a block, alternating, random, or graft copolymer.
In some embodiments, the thermoplastic polymer is crosslinkable. In more particular embodiments, the thermoplastic crosslinkable polymer behaves as a pliable thermoplastic material at relatively low temperature during deposition of the precursor material, while being able to transform into a hardened durable non-pliable thermoset state after deposition and construction of the magnetic object. The thermoplastic crosslinkable polymer (i.e., polymeric binder) has a characteristic of a delayed crosslinking reaction to the extent that a majority of the crosslinking occurs after the solid precursor material has been melted, extruded, and deposited on a substrate. By virtue of this crosslinking ability, the polymeric binder functions initially as a thermoplastic and then as a thermoset after crosslinking. Thus, the polymeric binder can be considered a hybrid polymer, i.e., having characteristics of both a thermoplastic and a thermoset. However, at the thermoset stage, the polymeric binder forms a three-dimensional covalent network, and thus, cannot revert back to a thermoplastic state, as expected for a thermoset polymer. In some embodiments, the thermoplastic polymer is not crosslinkable.
In order to possess this hybrid characteristic, the polymeric binder possesses groups that ultimately undergo crosslinking, either with the same or other groups in the same polymer, or with the same or other groups in a different polymer or compound (e.g., a rapid or latent crosslinking agent) that has been admixed with the polymeric binder. In conventional fused deposition modeling (FDM), the polymer feed material is simply melted and extruded directly onto a cold or warm plate, or onto a prior build layer. These applications require materials that are spatially locked in place immediately after deposition and maintain tolerance during thermal cycling. Since out-of-the-box heating requires localized deposition of energy to promote layer-to-layer bonding, part distortion is a limiting factor when building high strength components.
The hybrid polymers exhibit a broad thermal activation window that facilitates rapid pre-polymer formation at slightly elevated temperatures without full crosslinking. The hybrid polymer is preferably a reactive polymer, such as polyurethane and/or epoxy, which may be reacted with rapid or latent crosslinking agents, such as moisture provided by a humid environment in the case of urethanes, or an aromatic amine and a polyphenol in the case of epoxies. Typical FDM employs a three-step process, namely, melt, deposit and solidify, while embodiments of this invention can include a five-step process: melt, partially crosslink to achieve desired viscosity, deposit, solidify, and initiate extensive crosslinking. In other embodiments, application of an electromagnetic field can also be used to align aromatic polymer structures for crosslinking between layers. The formation of chemical bonds across layers can improve z-strength and enable incorporation of a large fraction of second phase reinforcements, such as carbon fiber, both of which are currently limited in polymer 3D printing. The crosslinkable polymers used in the method of this invention also provide the advantage of chemically bonding (crosslinking) layers with underlying or previously deposited layers to improve inter-layer adhesion and strength of the deposited part.
The hybrid crosslinkable polymers can minimize distortion during a build, increase layer-to-layer adhesion, and/or minimize anisotropy in the part that results from poor interlayer adhesion. The traditional thermoplastic approach with FDM relies on the molten extruded material to solidify on top of a previous deposit, which is typically held at an elevated temperature, but well below the melting temperature of the material. In this condition, the interaction between the newly extruded material and previous deposit is minimal, as there is very little penetration and entanglement of molecules from the molten material into the previous deposit. Even when the previous deposit is held at an elevated temperature, the surface may become “tacky,” but the intermolecular bonding between the deposition layers remains low.
Using the hybrid polymers, the solidification process is a chemically driven polymerization process, rather than solely a thermally driven phase change as with thermoplastics. Hybrid polymers possess unique rheological characteristics well suited for additive manufacturing of bonded permanent magnets. As discussed above, the hybrid polymers are solid at room temperature and melt at elevated temperatures, yet can crosslink to form a thermoset. In embodiments of this invention, these polymers act as thermoplastics during deposition, and as thermosets after deposition. During the conventional deposition of thermosets, a monomer material is deposited in liquid form, and the crosslinking process that solidifies the thermoset material is irreversible and may be driven by time, heat, a chemical reaction, and/or irradiation. In the case of additive manufacturing according to embodiments of this invention, the concept is to crosslink the material using a chemical reaction and maintain a low temperature gradient within the part. The catalyst that initiates the crosslinking process may be, for example, a secondary chemical mixed with the deposited material during or just prior to deposition, or the crosslinking may be initiated with exposure to air.
Exemplary hybrid polymers include, for example, polyurethanes, epoxy-containing polymers, and polymers containing vinyl acetate units. The hybrid polymer may include a backbone and/or pendant groups that are aromatic, in which case the hybrid polymer may be referred to as an “aromatic polymer”. In embodiments of this invention, the polymer material is prepared with a rapid or latent crosslinking agent, such as moisture provided by a humid environment in the case of urethanes, or an aromatic amine and/or a polyphenol in the case of epoxies. The polymer can be blended with a limited quantity of a first curing agent to obtain a partially reacted pre-polymer at moderate temperatures, such as during melt extrusion, and a second less reactive curing agent, such as a phenolic curing agent, for higher temperature curing.
The particles having a hard magnetic material composition (i.e., “magnetic particles”) can have any suitable particle size, but typically no more than or less than 1 mm, 0.5 mm, 200 microns, 100 microns, 50 microns, 1 micron, 0.5 micron, 0.2 micron, or 0.1 micron, or a distribution of particles bounded by any two of these values. The magnetic particles can be, for example, nanoparticles (e.g., 1-500 nm) or microparticles (e.g., 1-500 microns). The term “hard magnetic material composition” refers to any of the ferromagnetic or ferrimagnetic compositions, known in the art, that exhibit a permanent magnetic field with high coercivity (i.e., without a continuous current supply), generally at least or above 300, 400, or 500 Oe. Thus, the magnetic particles considered herein are not paramagnetic or superparamagnetic particles. The magnetic particles may be magnetically isotropic or anisotropic, and may have any desired shape, e.g., substantially spherical, ovoid, filamentous, or plate-like.
Typically, the permanent magnet composition is metallic or a metal oxide, and often contains at least one element selected from iron, cobalt, nickel, copper, gallium, and rare earth elements, wherein the rare earth elements are generally understood to be any of the fifteen lanthanide elements along with scandium and yttrium. In particular embodiments, the permanent magnet composition includes iron, such as magnetite, lodestone, or alnico. In other particular embodiments, the permanent magnet composition contains at least one rare earth element, particularly samarium, praseodymium, and/or neodymium. A particularly well-known samarium-based permanent magnet is the samarium-cobalt (Sm—Co alloy) type of magnet, e.g., SmCo5 and Sm2Co17. A particularly well-known neodymium-based permanent magnet is the neodymium-iron-boron (Nd—Fe—B) type of magnet, typically having the formula Nd2Fe14B. Other rare earth-containing hard magnetic material compositions include, for example, Pr2Co14B, Pr2Fe14B, and Sm—Fe—N. The hard magnet material may or may not have a composition that excludes a rare earth metal. Some examples of non-rare earth hard magnetic materials include MnBi, AlNiCo, and ferrite-type compositions, such as those having a Ba—Fe—O or Sr—Fe—O composition. Particle versions of such magnetic compositions are either commercially available or can be produced by well-known procedures, as evidenced by, for example, P. K. Deheri et al., “Sol-Gel Based Chemical Synthesis of Nd2Fe14B Hard Magnetic Nanoparticles,” Chem. Mater., 22 (24), pp. 6509-6517 (2010); L. Y. Zhu et al., “Microstructural Improvement of NdFeB Magnetic Powders by the Zn Vapor Sorption Treatment,” Materials Transactions, vol. 43, no. 11, pp. 2673-2677 (2002); A. Kirkeminde et al., “Metal-Redox Synthesis of MnBi Hard Magnetic Nanoparticles,” Chem. Mater., 27 (13), p. 4677-4681 (2015); and U.S. Pat. No. 4,664,723 (“Samarium-cobalt type magnet powder for resin magnet”). The permanent magnet composition may also be a rare-earth-free type of magnetic composition, such as a Hf—Co or Zr—Co alloy type of permanent magnet, such as described in Balamurugan et al., Journal of Physics: Condensed Matter, vol. 26, no. 6, 2014, the contents of which are herein incorporated by reference in their entirety. In some embodiments, any one or more of the above-described types of magnetic particles are excluded from the precursor material and resulting bonded permanent magnet produced after additive manufacturing.
The magnetic particles are generally included in the solid precursor material in an amount of at least or above 20 wt. % by weight of the polymer binder and magnetic particles (or alternatively, by weight of the solid precursor material). In different embodiments, the magnetic particles are included in an amount of at least or above 20, 30, 40, 50, 60, 70, 80, 90, 92, 95, or 98 wt. %, or in an amount within a range bounded by any two of the foregoing values. Alternatively, the magnetic particles are included in the solid precursor material in an amount of at least or above 40, 45, 50, 55, 60, 65, 70, 75, or 80 vol %.
In some embodiments, the solid precursor material may or may not further include non-magnetic particles having a composition that confers additional tensile strength to the bonded magnetic after curing. The non-magnetic particles can be composed of, for example, carbon, metal oxide, or metal carbon particles. The particles may have any suitable morphology, including, for example, spheroidal particles or filaments. The particles may be present in the solid precursor material in any desired amount, e.g., at least or above 1, 2, 5, 10, 20, 30, 40, or 50 wt. %, or in an amount within a range bounded by any two of the foregoing values. The term “filament,” as used herein, refers to a particle having a length dimension at least ten times its width dimension, which corresponds to an aspect ratio (i.e., length over width) of at least or above 10:1 (i.e., an aspect ratio of at least 10). In different embodiments, the filament has an aspect ratio of at least or above 10, 20, 50, 100, 250, 500, 1000, or 5000. In some embodiments, the term “filament” refers only to particles having one dimension at least ten times greater than the other two dimensions. In other embodiments, the term “filament” also includes particles having two of its dimensions at least ten times greater than the remaining dimension, which corresponds to a platelet morphology. Notably, the magnetic particles may also (and independently) have a spheroidal, platelet, or elongated (e.g., filamentous) morphology. In some embodiments, the magnetic particles are filaments having any of the aspect ratios described above. Notably, magnetic particles having an anisotropic (e.g., elongated or filamentous) shape are generally more amenable to alignment in a directional magnetic field.
In particular embodiments, carbon filaments are included in the solid precursor material. The carbon filaments can be, for example, carbon fibers, carbon nanotubes, platelet nanofibers, graphene nanoribbons, or a mixture thereof. In the case of carbon fibers, these may be any of the high-strength carbon fiber compositions known in the art. Some examples of carbon fiber compositions include those produced by the pyrolysis of polyacrylonitrile (PAN), viscose, rayon, lignin, pitch, or polyolefin. The carbon nanofibers may also be vapor grown carbon nanofibers. The carbon fibers can be micron-sized carbon fibers, generally having inner or outer diameters of 1-20 microns or sub-range therein, or carbon nanofibers, generally having inner or outer diameters of 10-1000 nm or sub-range therein. In the case of carbon nanotubes, these may be any of the single-walled or multi-walled carbon nanotubes known in the art, any of which may or may not be heteroatom-doped, such as with nitrogen, boron, oxygen, sulfur, or phosphorus. The carbon filament, particularly the carbon fiber, may possess a high tensile strength, such as at least 500, 1000, 2000, 3000, 5000, or 10,000 MPa. In some embodiments, the carbon filament, particularly the carbon fiber, possesses a degree of stiffness of the order of steel or higher (e.g., 100-1000 GPa) and/or an elastic modulus of at least 50 Mpsi or 100 Mpsi.
In other embodiments, metal oxide filaments may or may not be included in the solid precursor material. The metal oxide filaments (also known as metal oxide nanowires, nanotubes, nanofibers, or nanorods), if present, can be, for example, those having or including a main group metal oxide composition, wherein the main group metal is generally selected from Groups 13 and 14 of the Periodic Table. Some examples of Group 13 oxides include aluminum oxide, gallium oxide, indium oxide, and combinations thereof. Some examples of Group 14 oxides include silicon oxide (e.g., glass), germanium oxide, tin oxide, and combinations thereof. The main group metal oxide may also include a combination of Group 13 and Group 14 metals, as in indium tin oxide. In other embodiments, the metal oxide filaments have or include a transition metal oxide composition, wherein the transition metal is generally selected from Groups 3-12 of the Periodic Table. Some examples of transition metal oxides include scandium oxide, yttrium oxide, titanium oxide, zirconium oxide, hafnium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, iron oxide, ruthenium oxide, cobalt oxide, rhodium oxide, iridium oxide, nickel oxide, palladium oxide, copper oxide, zinc oxide, and combinations thereof. The metal oxide filament may also include a combination of main group and transition metals. The metal oxide filament may also include one or more alkali or alkaline earth metals in addition to a main group or transition metal, as in the case of some perovskite nanowires, such as CaTiO3, BaTiO3, SrTiO3, and LiNbO3 nanowires, and as further described in X. Zhu, et al., J. Nanosci. Nanotechnol., 10(7), pp. 4109-4123, July 2010, and R. Grange, et al., Appl. Phys. Lett., 95, 143105 (2009), the contents of which are herein incorporated by reference. The metal oxide filament may also have a spinel composition, as in Zn2TiO4 spinel nanowires, as described in Y. Yang et al., Advanced Materials, vol. 19, no. 14, pp. 1839-1844, July 2007, the contents of which are herein incorporated by reference. In some embodiments, the metal oxide filaments are constructed solely of metal oxide, whereas in other embodiments, the metal oxide filaments are constructed of a coating of a metal oxide on a non-metal oxide filament, e.g., silica-coated or germanium oxide-coated carbon nanotubes, as described in M. Pumera, et al., Chem Asian J., 4(5), pp. 662-667, May 2009, and M. Pumera, et al., Nanotechnology, 20(42), 425606, 2009, respectively, the contents of which are herein incorporated by reference. The metal oxide layer may alternatively be disposed on the surface of a metallic filament. The metal oxide filaments may also have any of the lengths and diameters described above.
In other embodiments, metal filaments may or may not be included in the solid precursor material. The metal filaments (also known as metal nanowires, nanotubes, nanofibers, or nanorods), if present, can be, for example, those having or including a main group metal composition, such as a silicon, germanium, or aluminum composition, all of which are well known in the art. The metal filaments can also have a composition having or including one or more transition metals, such as nickel, cobalt, copper, gold, palladium, or platinum nanowires, as well known in the art. The metal filaments may also be doped with one or more non-metal dopant species, such as nitrogen, phosphorus, arsenic, or silicon to result in a metal nitride, metal phosphide, metal arsenide, or metal silicide composition. Many of these doped metal compositions are known to have semiconductive properties.
The solid precursor material may or may not also include an anti-oxidant compound. The anti-oxidant is generally of such composition and included in such amount as to help protect the magnetic particles from oxidizing during the additive manufacturing process. In some embodiments, the anti-oxidant is a phenolic compound, such as phenol or a substituted phenol (e.g., 2,6-di-t-butyl-4-methylphenol). In other embodiments, the anti-oxidant is a complexant molecule, such as EDTA. The anti-oxidant is typically included in the solid precursor material in an additive amount, typically up to or less than 5, 2, or 1 wt. %.
In some embodiments, the solid precursor material may or may not include one or more additional components that desirably modulate the physical properties of the resulting melt. In particular embodiments, a plasticizer is included in the precursor material, typically to promote plasticity (i.e., fluidity) and to inhibit melt-fracture during the extrusion and deposition process. The one or more plasticizers included in the precursor material can be any of the plasticizers well known in the art and appropriate for the particular polymer being extruded. For example, in a first embodiment, the plasticizer may be a carboxy ester compound (i.e., an esterified form of a carboxylic or polycarboxylic acid), such as an ester based on succinic acid, glutaric acid, adipic acid, terephthalic acid, sebacic acid, maleic, dibenzoic acid, phthalic acid, citric acid, and trimellitic acid. In a second embodiment, the plasticizer may be an ester-, amide-, or ether-containing oligomer, such as an oligomer of caprolactam, wherein the oligomer typically contains up to or less than 10 or 5 units. In a third embodiment, the plasticizer may be a polyol (e.g., a diol, triol, or tetrol), such as ethylene glycol, diethylene glycol, triethylene glycol, glycerol, or resorcinol. In a fourth embodiment, the plasticizer may be a sulfonamide compound, such as N-butylbenzenesulfonamide, N-ethyltoluenesulfonamide, or N-(2-hydroxypropyl)benzenesulfonamide. In a fifth embodiment, the plasticizer may be an organophosphate compound, such as tributyl phosphate or tricresyl phosphate. In a sixth embodiment, the plasticizer may be an organic solvent. The organic solvent considered herein is a compound that helps to soften or dissolve the polymer and is a liquid at room temperature (i.e., a melting point of no more than about 10, 20, 25, or 30° C.). Depending on the type of polymer, the organic solvent may be, for example, any of those mentioned above (e.g., ethylene glycol or glycerol), or, for example, a hydrocarbon (e.g., toluene), ketone (e.g., acetone or butanone), amide (e.g., dimethylformamide), ester (e.g., methyl acetate or ethyl acetate), ether (e.g., tetrahydrofuran), carbonate (e.g., propylene carbonate), chlorohydrocarbon (e.g., methylene chloride), or nitrile (e.g., acetonitrile). In some embodiments, one or more classes or specific types of any of the above plasticizers are excluded from the melt. In some embodiments, the plasticizer or other auxiliary component may be removed from the extrudate by subjecting the extrudate to a post-bake process that employs a suitably high temperature capable of volatilizing the plasticizer or other auxiliary component.
In the method described herein, the solid precursor material containing the polymeric binder and magnetic particles is incorporated (fed) into one or more deposition heads of a BAAM system. Within the deposition head, the precursor material is melted and compounded before being extruded from an orifice of the deposition head. The extrudate, when exiting the orifice of the deposition head, is at a temperature above the glass transition temperature (Tg) of the precursor material. In some embodiments, in order to avoid a temperature that could denature the magnetic particles, the precursor material is heated to a temperature of no more than 5° C., 10° C., 15° C., or 20° C. above the glass transition temperature of the precursor material. Notably, the glass transition temperature of the precursor material is to be distinguished from the glass transition temperature or melting point of the thermoplastic polymer. In different embodiments, an extrudate of the precursor material exits the deposition head (and/or is initially deposited) at a temperature of at least 120° C., 130° C., 140° C., 150° C., 160° C., 165° C., 170° C., 175° C., 180° C., 185° C., 190° C., 195° C., 200° C., 225° C., 250° C., 275° C. or 300° C., or a temperature within a range bounded by any two of the foregoing exemplary temperatures.
The melt is extruded through a nozzle of the deposition head and deposited onto a platform from which the object will be removed, or the extrudate is deposited onto an existing portion of the object being manufactured to which the extrudate is being bonded. The extrudate is deposited layer-by-layer from the one or more deposition heads until an object is formed from the extrudate. As the extrudate exits the nozzle and is deposited, the extrudate cools, which results in solidification. In the case where a crosslinkable polymer is included in the extrudate, the deposition and cooling process leads to an increase in viscosity and a transition of the extrudate to a semi-solid or gel (i.e., a “solidified preform”). At this stage, an initial substantially incomplete level of crosslinking typically also occurs, before final hardening over time.
In some embodiments, as the extrudate exits the nozzle and is being deposited, the extrudate is exposed to a directional (external and non-varying) magnetic field of sufficient strength to align the particles having a hard magnetic composition. The alignment of the magnetic particles refers to at least an alignment of the individual magnetic fields (or poles) of the magnetic particles. In the case of anisotropically shaped magnetic particles, the alignment also involves a physical alignment, e.g., axial alignment of filamentous particles. In the case of a thermoplastic polymer containing aromatic groups, the polymer may also undergo alignment in the presence of a magnetic field by virtue of aligning and stacking of the aromatic groups. As the magnetic particles and/or thermoplastic polymer require an appreciable degree of freedom of movement to align themselves, the exposure to the directional magnetic field should occur at least during the time the precursor material is in a melted or partially melted form, i.e., before final solidification. Generally, in order for magnetic particles and/or thermoplastic polymer to sufficiently re-orient and align in the melt, the extrudate melt should possess a melt viscosity of up to or less than 20,000, 50,000, or 100,000 cPs, where cPs refers to a centipoise. However, in order to ensure that the extrudate maintains a shape when deposited, the melt on deposition should have a viscosity of at least 1,000, 2,000, 5,000, or 10,000 cPs. In order to sufficiently align the magnetic particles and/or thermoplastic polymer, the external magnetic field should generally have a magnetic field strength of at least 0.25 or 0.5 Tesla (0.25 T or 0.5 T). In different embodiments, the external magnetic field has a magnetic field strength of about, at least, above, up to, or less than, for example, 0.25, 0.5, 1, 1.2. 1.5, 2, 2.5, 3, 3.5, 4, 5, 6, 7 or 8 T.
In some embodiments, the extrudate after deposition is cooled over time, which leads to hardening and production of the hard magnetic bonded object. In the case where a crosslinkable polymer is included in the extruded, after the extrudate is deposited, and generally but not necessarily after a complete object of desired shape is constructed with the solidified preform, the solidified preform is cured by subjecting the solidified preform to conditions that result in substantial crosslinking to the extent that the thermoplastic behavior of the solidified preform transitions to thermoset behavior. At the curing stage, the transition to a thermoset generally coincides with an increase in viscosity of the solidified preform to a value substantially above 100,000 cPs, and typically, a value of at least or above 200,000, 500,000, or 1,000,000 cPs, and eventually, a transition to a completely non-flowable solid that may be characterized by the usual properties of a solid, e.g., tensile strength and elasticity.
In some embodiments, substantially complete crosslinking occurs by allowing the solidified preform to cool over time. The length of time may be any suitable period of time (e.g., hours or days) for the solidified preform to undergo substantially complete crosslinking. In other embodiments, the solidified preform is subjected to an energetic source that promotes or induces crosslinking. The energetic source may be, for example, thermal energy, electromagnetic irradiation (e.g., ultraviolet, x-ray or gamma-ray energy), or ion bombardment (e.g., electron or neutron beam irradiation).
The shape of the object that is ultimately built can be suited to any application in which a magnetic material having a significant degree of mechanical strength is desired, such as electrical motors. Although the shape of the magnetic material ultimately produced can be simple, e.g., a planar object, such as a film or coating of a desired two-dimensional shape (e.g., square or disc), the additive manufacturing process is primarily suited to the production of complex (i.e., intricate) shapes. Some examples of intricate shapes include rings, filled or unfilled tubes, filled or unfilled polygonal shapes having at least or more than four vertices, gears, and irregular (asymmetric) shapes. Other possible shapes include arcs with an angle greater than 90 degrees and less than 180 degrees, preferably in the range 120-160 degrees. The object may also be, for example, a functional motor, engine, or turbine.
In some embodiments, the bonded permanent magnet is coated with a polymer that functions to reduce exposure of the bonded permanent magnet to oxygen. The coating polymer can be, for example, an epoxy-based or silica-based polymer or hybrid thereof. In some embodiments, the coating polymer is a sol gel type of polymer, which may be a hybrid organic-inorganic polymer.
Examples have been set forth below for the purpose of illustration and to describe certain specific embodiments of the invention. However, the scope of this invention is not to be in any way limited by the examples set forth herein.
Big Area Additive Manufacturing (BAAM) Process
Three dimensional printing was performed at Manufacturing Demonstration Facility at Oak Ridge National Laboratory with the Big Area Additive Manufacturing (BAAM) system with a build volume of 3.56 m×1.65 m×0.86 m. The main components of the BAAM include the gantry system, single screw extruder, and a heated bed. The gantry uses linear drive motors to position the extruder with ±0.0254 mm accuracy and was operated at a constant velocity of 25.4 mm/s during the printing process. The extruder is 25 mm in diameter with an aspect ratio of 12 (i.e. length/diameter=12) and is used to melt nylon NdFeB composite pellets and deposit molten materials at a rate consistent with the gantry movement and desired bead profile.
The temperature at the orifice exit of the extruder was approximately 270° C. The first layer was deposited on an acrylonitrile butadiene styrene (ABS) sheet that was placed on top of the heated aluminum table kept at a constant temperature of 90° C. A hollow cylinder shape with an OD×ID of 4.5″×3″ of NdFeB (as shown in
Magnetic Properties of the Bonded Permanent Magnet
The room temperature magnetization data obtained on the BAAM and injection molded bonded magnets are shown in
The energy product (BH)max quantifies the magnetostatic energy a permanent magnet material can store therefore characterizes how strong the magnet is. The ideal M-H hysteresis loops for a permanent magnet should be square-shaped, which gives a (BH)max=¼ μ0Js2, where Js=4πMs is the saturation magnetization in unit of gauss. The M-H loops of real permanent magnet materials deviate from ideal shape, as shown in
In real applications, the magnets are frequently exposed to elevated temperatures. Therefore, the magnetic properties of the BAAM fabricated magnets were analyzed in the temperature interval of 300 K to 400 K.
Flux Aging Loss of the Bonded Permanent Magnet
Microstructural Analysis
Mechanical Properties of the Bonded Permanent Magnet
Polyphenylene-sulfide (PPS) and polyamide (Nylon) are the two commonly used polymer binders for bonded magnets production. It has been found that PPS based magnets usually exhibit higher ultimate strengths, higher temperature operation but lower ductility than Nylon based magnets (Garrell et al., Mater. Sci. Eng. A, 359, 375-383, 2003). The Nylon polymer used in this work is Nylon-12, which is a thermoplastic binder with a melting point of 177° C. This type of binder usually offers the material superior mechanical flexibility and improves corrosion resistance (Ormerod et al., J. Appl. Phys., 4816, 81, 1997).
To investigate the failure mechanism, the fracture surfaces after tensile tests were examined with SEM, as shown in
Bonded Permanent Magnet with 70 vol % Nd—Fe—B powder
To compete with injection and compression molding, which are the established methods to fabricate complex-shaped isotropic bonded magnets, an effort was made to increase the loading fraction of the magnet powder in the nylon binder in the 3D printing process to increase the magnetic strength. In this study, 70 vol. % nylon bonded Nd—Fe—B magnets were printed into various shapes. In addition, the as-printed magnets were coated with two types of epoxy-based polymers to improve their thermal stability. The microstructure, magnetic and mechanical properties, flux aging loss, and eddy current loss are reported below. The performance of the 3D printed magnets in a DC motor configuration was also demonstrated.
Computer-aided design (CAD) software was used as the first step of the 3D printing manufacturing process. The Big Area Additive Manufacturing (BAAM) printer took instructions from a CAD file to guide the printhead for layer-by-layer growth during the printing process. The geometric designs were created and saved as standard triangle language (.STL) files, which were then “sliced” in the printer software, which created the layers and path for each layer. Composite pellets made of 70 vol. % isotropic MQPB+ powder and 30 vol. % polyamide were used as the feedstock materials for the BAAM system. The material was deposited at 255° C. onto a heated print bed kept at ˜95° C. The preheating of the bed was used to enhance the bonding between layers as the beads are bonded together primarily via thermal fusion, which depends on the temperature, viscosity, and surface area. The nozzle diameter was 0.3 inch, the layer thickness was 0.15 inch, and the printing speed was 1 inch/second. The nozzle was equipped with a z-tamping attachment to obtain a leveled surface, and to strengthen the bonding between layers. More details about the compounding process of the pellet feed and the print parameters have been reported previously (L. Li, et al., Sci. Rep. 6, 36212, 2016).
The magnetic hysteresis loops were measured from 20 to 120° C.; using a closed loop magnetic hysteresis graph measurement system. Cross-sections of the as-printed sample and fractured surface were examined by scanning electron microscopy. Flux measurements were conducted using Helmholtz Coils with a fluxmeter. The samples were magnetized at 9 Tesla and then aged at elevated temperatures. The as-printed samples were treated with two types of polymer coatings to improve the thermal stability. The first type is a 3M Scotch-Weld™ DP100 epoxy (Process I), and the second type is a high temperature silica ceramic VHT™ coating (Process II). Tensile tests were performed with a screw-driven tensile testing machine at an engineering strain rate of 10−3s−1 and temperatures of 20 and 100° C., in ambient air. Dog bone shaped samples with gauge dimension of 3.1×1.5×12.7 mm3 were used in all testing. Since the plastic deformation is limited, only the ultimate tensile stress was determined, which is calculated by the maximum load divided by the original cross-section area. Eddy current losses were estimated from AC susceptibility measurements. Resistivity measurements were achieved using a four-probe resistivity measurement setup. The 70 vol. % BAAM magnets were installed into a 12 V-750 RPM-DC motor and evaluated.
Table 3 (below) summarizes the magnetic characteristics of the 70 vol. % BAAM magnets at elevated temperatures up to 120° C. It is not surprising that all the characteristics decrease with increasing temperatures. The magnetic performance with increasing temperature can be evaluated from the temperature coefficients of Br, Hci and (BH)max, which are, as shown in Table 3, −0.18%/° C., −0.33%/° C., and −0.36%/° C., respectively. These values are also close to the reported thermal coefficients for MQPB+ powders (Ma et al., supra). In fact, the primary drawback of Nd—Fe—B magnets is the unsatisfactory magnetic performance at elevated temperatures, which is related to the relatively high temperature coefficients of Br and Hci, leading to a rapid deterioration in the intrinsic coercivity and flux density. Therefore, Sm—Co magnets are frequently adopted when high temperature operation is needed.
The thermal stability of magnets can also be compared by measuring the room temperature flux density of the samples before and after aging at elevated temperatures. The flux loss is related to a magnetization reversal mechanism occurring with rising temperature (Brown et al., J. Magn. Magn. Mater., 248(3), 432-440, 2002). The total flux loss is composed of recoverable loss and irreversible loss, and the latter is due to the oxidation of the Nd—Fe—B powder (Brown et al., supra). The percentage of flux loss at a certain temperature is a direct reflection of the thermal stability of the magnet. The flux aging loss with time for the as-printed 70 vol. % BAAM magnets is presented in
One way to improve thermal stability in a bonded magnet is to prevent the magnet from being oxidized by including a protective layer either on the individual powders or on the whole magnet. In this study, the as-printed 70 vol. % BAAM magnets were coated with two types of polymers (Process I and Process II), and the flux aging loss was compared for the treated and as-printed samples, and the maximum operating temperatures were determined. Process I is a 3M Scotch-Weld™ DP100 room-temperature cured epoxy, which is commercially available and widely used due to its affordability and temperature capabilities. Process II is a high temperature silica ceramic VHT™ coating.
Even though sintered magnets offer high residual magnetic flux density which contributes to a high torque for a motor magnet, the high eddy current loss resulting from a high electrical conductivity leads to lower efficiency converting energies between magnetic and mechanical. In the present study, eddy current losses are estimated from AC magnetic susceptibility measurements where both the real (M′) and imaginary (M″) parts are measured. The imaginary part of the susceptibility M″, corresponds to dissipative losses in the sample which can result in substantial heating. In electrical conductors, the dissipation is due to eddy currents, but in ferromagnets there are additional losses such as losses due to irreversible domain wall motion or hysteresis loss.
To test the applicability of the 70 vol. % BAAM magnets for motor applications, existing two arc segments of sintered ferrite magnet in a DC motor were replaced with BAAM magnets. A mounting piece was designed and 3D printed to securely hold the motors and keep the shafts concentric. The motors' back electromotive force (back-EMF) were tested in a back-to-back fashion.
In summary, the present disclosure has described a BAAM process to fabricate near-net-shape isotropic NdFeB bonded magnets. Magnetic and mechanical characterizations demonstrate that the BAAM fabricated magnets can compete with or outperform the injection molded magnets. In addition, additive manufacturing offers significant advantages such as cost effectiveness (no tooling required), fast speed (simple procedure), and capability of producing parts of unlimited in sizes and shapes. Therefore, BAAM provides an effective method in realizing arbitrary shape with minimum cost and waste, and has the potential to revolutionize large-scale industry production of bonded magnets.
The ability to create a near-net shaped magnet results in less post processing, less (nearly zero) waste generation, and a wide range of applications for a single manufacturing platform. In the above example, nylon-bonded Nd—Fe—B magnets with a high loading fraction of 70 vol. % were fabricated via an extrusion-based additive manufacturing process for the first time. The printed magnets exhibited superior magnetic properties, compared to injection molded magnets, while maintaining substantial geometry flexibility. Motors installed with the BAAM-produced printed magnets exhibited similar performance as compared to those installed with sintered ferrites. In addition, the extrusion-based additive manufacturing method via the BAAM system can be widely applied to net-shape manufacture other functional magnets, such as SmCo, SmFeN, Fe16N2, ferrites, and hybrids of more than one composition with binder materials such as nylon, PPS (polyphenylene sulfide), and other high temperature thermoplastics.
While there have been shown and described what are at present considered the preferred embodiments of the invention, those skilled in the art may make various changes and modifications which remain within the scope of the invention defined by the appended claims.
The present application claims benefit of U.S. Provisional Patent Application No. 62/413,643, filed on Oct. 27, 2016, all of the contents of which are incorporated herein by reference.
This invention was made with government support under Prime Contract No. DE-AC05-00OR22725 and DE-AC02-07CH11358 awarded by the U.S. Department of Energy. The government has certain rights in the invention.
| Number | Date | Country | |
|---|---|---|---|
| 62413643 | Oct 2016 | US |
