The present invention relates permanent magnets, and more particularly, this invention relates to YCo5-based magnets.
Among the great challenges of materials science is discovering a material that satisfies conflicting requirements and also possesses specific properties for a particular application. There is a need for strong permanent magnets to withstand higher temperatures, for example Curie temperatures ranging from 800 K to 1200 K, which the widely used neodymium-based magnets (Nd2Fe14B, Neomax®) cannot tolerate. Pure Samarium-Cobalt (SmCo) magnets (both SmCo5 and Sm2Co17) satisfy this requirement and are less subject to corrosion than the neodymium-based magnets and thus do not require a coating. Moreover, pure SmCo magnets have strong resistance to demagnetization.
Three basic material parameters determine the intrinsic properties of hard magnetic materials: (i) spontaneous (saturation) magnetization, (Ms), (ii) Curie temperature (Tc), and (iii) magnetocrystalline anisotropy energy (MAE). An optimal technological permanent magnet has a large spontaneous magnetization (Ms≥˜1 MA), high Curie temperature (Tc≥˜550 K), and large MAE constant (K1≥˜4 MJ/m3).
Pure YCo5 permanent magnets exhibit high uniaxial MAE constant of K1˜6.5 MJ/m3, which is excessive compared to that of Nd2Fe14B magnets having MAE with a K1 of ˜4.9 MJ/m3. YCo5 permanent magnets have high Curie temperature, Tc˜987 K, which is almost twice that of Nd2Fe14B magnets having Curie temperature, Tc˜588 K. However, the Nd2Fe14B magnet currently dominates the world market for permanent magnets (˜62% of world market), since the Nd2Fe14B magnet has large spontaneous magnetization and possesses the highest energy performance measured by a record high energy product. The Maximum Energy Product (BH)max of the Nd2Fe14B magnet at 512 kJ/m3 is more than twice as high as the (BH)max of YCo5 magnets, at 224 kJ/m3.
It would be desirable to formulate a permanent magnet with a greater spontaneous magnetization, high MAE and thermostability comparable to YCo5 magnets while having a high Curie temperature.
In accordance with one aspect of the presently disclosed inventive concepts, a magnet includes a material having a chemical formula: YFe3(Ni1-xCox)2, where x is greater than 0 and x is less than 1.
In accordance with another aspect of the presently disclosed inventive concepts, a magnet includes a material having a chemical formula: YFe3(Ni1-xCox)2, where x is greater than 0 and x is less than 1, and where the material has a CuCa5-type crystal structure.
Other aspects and advantages of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the drawings, illustrate by way of example the principles of the invention.
The following description is made for the purpose of illustrating the general principles of the present invention and is not meant to limit the inventive concepts claimed herein. Further, particular features described herein can be used in combination with other described features in each of the various possible combinations and permutations.
Unless otherwise specifically defined herein, all terms are to be given their broadest possible interpretation including meanings implied from the specification as well as meanings understood by those skilled in the art and/or as defined in dictionaries, treatises, etc.
It must also be noted that, as used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless otherwise specified.
The term “dopant” as used in the instant descriptions shall be understood to encompass any element or compound that is included in a host medium material, so as to convey a particular functional characteristic or property on the resulting structure. In most cases, the dopant will be incorporated into a crystal structure of the host medium material.
In accordance with one general aspect of the presently disclosed inventive concepts, a magnet includes a material having a chemical formula: YFe3(Ni1-xCox)2, where x is greater than 0 and x is less than 1.
In accordance with another general aspect of the presently disclosed inventive concepts, a magnet includes a material having a chemical formula: YFe3(Ni1-xCox)2, where x is greater than 0 and x is less than 1, and where the material has a CuCa5-type crystal structure.
A list of acronyms used in the description is provided below.
According to various inventive concepts described herein, a permanent magnet may be formed that has a high spontaneous magnetization, thermostability, high Curie temperatures and high magnetocrystalline anisotropy energy (MAE). Ideally, transition-metal dopants may boost the energy product of YCo5 magnets without compromising the high MAE and high Curie temperatures of these magnets. For example, combining transition-metal (TM) with rare-earth-metal (RE) atoms in various intermetallic compounds may result in material in which RE and TM atoms induce a large magnetic anisotropy and provide a large magnetization and high Curie temperature.
Iron (Fe) is more readily available than cobalt (Co) such that Fe is ˜2000 times more abundant in the Earth's crust than Co. Thus, at least from a cost standpoint, it would be beneficial to substitute Co atoms in YCo5 with Fe atoms since the relative abundance of available Fe could result in a less expensive component. In addition, Fe may be desirable as an added component to a magnet material since its ferromagnetic metal properties have a large magnetization at room temperature (1.76 MA/m).
As shown in
In the YFe5 compound that only includes Fe atoms without any Co atoms, the instability of the crystal structure may be related to a decrease in the number of 3d electrons in the electronic structure. Indeed, crystal stabilities of the magnetic 3d transition metals may be governed by the number of 3d electrons.
Thus, substituting all cobalt atoms with a transition metal with higher magnetic moment, such as iron, in order to optimize the maximum energy product (i.e., YCo5→YFe5) may result in a thermodynamically unstable crystal structure of an ordinary hexagonal phase. Moreover, YFe5 does not appear in the equilibrium Y—Fe phase diagram, although the alloy compound Y(Co1-xFex)5 with CaCu5-type structure has been synthesized for x=0.2 to 0.4.
For synthesized Y(Co1-xFex)5 materials, the Curie temperatures (Tc) for Y(Co1-xFex)5 alloys were found to increase from about 930 K to about 1020 K when increasing x from 0.0 to 0.2. In contrast, Y2(Co1-xFex)17 alloys exhibit a monotonic decrease in Curie temperature (Tc) with increasing Fe content. The orbital moment of cobalt is larger compared to iron, and a decrease of the MAE occurs for x>0. The lattice constant and magnetization are enhanced for x=0 to 0.4 in Y(Co1-xFex)5 alloys.
Accordingly, the inventive concepts presented herein, in several embodiments, involve ab initio calculations to add nickel (Ni) and iron (Fe) to a YCo5 magnet in order to stabilize Y(Co—Fe—Ni)5 alloys containing a sufficient amount of Fe to boost the energy product of the Y(Co—Fe—Ni)5 magnet.
In accordance with inventive concepts described herein, a magnet includes a material having a chemical formula: YFe3(Ni1-xCox)2, wherein x may be greater than 0 and x may be less than 1. In some approaches, the material may have a chemical formula: YFe3(Ni1-xCox)2, where x may be greater than 1−x such that the compound has a greater amount of Co compared to Ni. Accordingly, x may be a value between 0.5 and 1, such as 0.51, 0.52 . . . 0.98, 0.99. In other approaches, the material may have a chemical formula: YFe3(Ni1-xCox)2, where x may be less than 1−x, such that the compound has a greater amount of Ni compared to Co. Accordingly, x may be a value between 0 and 0.5, such as 0.01, 0.02 . . . 0.48, 0.49. Preferably, whether x is greater than or less than 1−x, the values are within a 10% difference of one another, e.g., x is a value in a range of 0.45-0.55. In preferred approaches, the material may have a chemical formula: YFe3(Ni1-xCox)2, where x is about equal to 1−x.
In at least one contemplated approach, in addition to iron and nickel, copper may be used to dope the YCo5 magnets as described herein. In contrast to the Y(Co1-xFex)5 system, Y(Co1-xNix)5 and Y(Co1-xCux)5 compounds are stable across the composition domain comprising x=0 to 1. Substituting cobalt atoms with nickel and/or copper atoms gradually decreases magnetization and magnetic anisotropy.
Preferably, the magnet as described in the inventive concepts herein includes a lower (e.g., reduced) amount of cobalt (up to 75% less Co) than the amount of Co in YCo5. Moreover, the magnet as described may be a permanent magnet.
The magnet compound of YFe3(Ni1-xCox)2 material as described herein may have a CaCu5-type crystal structure. Referring again to
In the inventive concepts described herein, a thermodynamically stable permanent magnet, for example having the chemical formula YFe3(Ni0.5Co0.5)2, may include no more than three Fe atoms per unit of the compound. Ideally, the Fe atoms would be distributed in the transition metal position 3g 106 nonequivalent atomic sites (as shown in
According to inventive concepts described herein, the addition of Ni to Y(Co1-xFex)5 magnets may stabilize the magnet. Transition metals have increasing 3d electron count in the following order: Fe<Co<Ni. Thus, replacing Co atoms with Fe atoms decreases the amount of 3d electrons in the compound, whereas replacing Co atoms with Ni atoms increases the amount of 3d electrons in the compound.
According to inventive concepts described herein, the resulting YFe3(Ni1-xCox)2 magnet may have a large energy product. State of the art electronic structure calculations confirmed that addition of Ni to YCo5 magnets stabilized Y(Co1-xFex)5 and maintained a reasonably high MAE comparable with the MAE of YCo5 magnets (see below in Experiments and Modeling Results).
According to inventive concepts described herein, a magnet with YFe3(Ni1-xCox)2 material includes Fe atoms, Ni atoms and the Co atoms which may be distributed in transition metal 2c 104 nonequivalent atomic sites. Moreover, high axial MAE may be obtained with energetically stable YFe3(Ni1-xCox)2 alloys using abundant and cost-effective Fe and Ni in place of expensive Co, and thereby achieving higher magnetic energy product compared to the YCo5 prototype compound. Some approaches may include a YFe3(Ni1-xCox)2 compound with partial ordering on the 2c-type 104 sites.
A magnet of YFe3(Ni1-xCox)2 includes a spin orientation of the Y atom that may be antiparallel to a spin orientation of the Fe, Ni, and Co atoms. The spin properties of the electrons in an atom generate a magnetic moment of the atom, as measured in terms of Bohr magneton (μB). Theoretical measurements of the YFe3(Ni1-xCox)2 magnet show magnetic moments of Y to be opposite atoms of each of the transition metals (e.g., Co, as shown below in Table 1).
Permanent magnets preferably include material with a high magnetocrystalline anisotropy energy (MAE). The MAE is the very small energy difference between phases with spin moments oriented in the easy and hard directions. The MAE may be defined by appropriate representation of the electronic and magnetic structures. In terms of uniaxial anisotropy, the MAE constant K1>0, where the MAE constant K1 is expressed in MJ/m3 units. The opposite case, K1<0, corresponds to the planar anisotropy. The magnitude of the MAE constant, K1, reflects the magnitude of MAE such that a larger positive value of K1 constant corresponds to a larger uniaxial MAE.
A magnet of YFe3(Ni1-xCox)2 may have a MAE that is about twice a MAE of Nd2Fe14B. In some approaches, a magnet of YFe3(Ni1-xCox)2 has a magnetocrystalline anisotropy energy constant (K1) that may be greater than about 10.6 MJ/m3.
In some approaches, the YFe3(Ni1-xCox)2 material may have a high MAE that may be comparable to the MAE of praseodymium (PrCo5), samarium (SmCo5), yttrium (YCo5) magnets of 8.1 MJ/m3, 17.2 MJ/m3 and 6.5 MJ/m3, respectively. The theoretical values of the YFe3(Ni1-xCox)2 compounds described herein were derived using novel computational material science approaches (see below in Experiments and Modeling Results).
It is desirable for a magnet material to have a high Curie temperature (Tc) in order to continue to function as a magnet under conditions with elevated temperatures. According to inventive concepts described herein, the material of the magnet YFe3(Ni1-xCox)2 has a Curie temperature (Tc) that may be about equal to a Curie Temperature of YCo5. In some approaches, the material of the magnet YFe3(Ni1-xCox)2 may have a Tc greater than or equal to about 1000 K.
Moreover, the YFe3(Ni1-xCox)2 compound may have a high magnetic energy product, comparable to neodymium-based magnets. The material of the magnet YFe3(Ni1-xCox)2 may have a maximum energy product of the material greater than or equal to about 351 kJ/m3. In one exemplary aspect, a YFe3CoNi magnet may have a maximum energy product of the material greater than about 309 kJ/m3. In various aspects, a YFe3CoNi magnet may have a maximum energy product of the material greater than or equal to about 300 kJ/m3.
In at least one exemplary aspect, a thermodynamically stable YFe3(Ni0.3Co0.7)2 magnet may be created by substituting up to an additional 30 at. % Ni for Co having a Tc of 900 K which is close to the calculated Tc of YCo5 magnet's Tc of 892 K. The YFe3(Ni0.3Co0.7)2 magnet may have a maximum energy product of the material greater than about 351 kJ/m3.
In another exemplary aspect, a YFe3Co2 magnet may be created having a Curie temperature Tc of 1098 K and a maximum energy product of 365 kJ/m3, according to various aspects described herein. The foregoing maximum energy product is about 71% of the maximum energy product for Nd2Fe14B magnets (e.g., 512 kJ/m3).
There are potentially many ways to produce the magnets described here, as would be readily apparent to one skilled in the art after reading the present disclosure. Any such method may be used to present the novel materials described herein.
An illustrative method to form a permanent magnet, which is presented by way of example only, may include starting with a YNi5 compound that is in a CaCu5-type structure. A maximum amount of Fe metal (e.g., ˜60 at %) may be dissolved with the YNi5 compound to form a stable YFe3Ni2 compound in the same structure modification where iron atoms predominantly occupy 3g sites of the crystal structure. In an ideal crystal structure, Fe atoms occupy all 3g positions.
The formation method may subsequently include gradual alloying of the YFe3Ni2 compound with Co, while keeping the amount of Y and Fe constant. In a preferred embodiment, up to 92% of the Ni atoms may be replaced with Co atoms.
Experiments and Modeling Results
YCo5 compounds crystallize in the hexagonal CaCu5-type structure with three non-equivalent atomic sites: Y1-(1a) 102, Co1-(2c) 104, and Co2(3g) 106 (see
Earlier neutron-diffraction studies of the Th(Co1-xFex)5 alloys (also based on the CaCu5-type structure) show that the larger Fe atoms preoccupies the 3g-type 106 sites, whereas the smaller Co atoms choose to occupy the 2c-type 104 sites. This occupational inclination has been affirmed by DFT calculations for YCo5 and SmCo5 compounds. In line with these calculations, the total energy for Fe at the 3g 106 site (E3g) is lower that than for Fe at the 2c 104 site (E2c) by 0.21 eV/f.u. and 0.10 eV/f.u. for YCo5 and SmCo5 magnets, correspondingly. If the YCo5 magnet is doped with Fe and Ni, Fe atoms occupy preferentially 3g 106 sites, while Ni atoms favor 2c 104 sites.
Nickel metal forms the stable CaCu5-type compounds with both yttrium and samarium metals. Calculated within EMTO formalism, the heat of formation of SmNi5 and YNi5 compounds (in the CaCu5-type structure) is −18.95 mRy/atom and −22.91 mRy/atom, correspondingly, which is in accord with the experimental measurements of −23.08 mRy/atom (−30.3 kJ/mole, SmNi5) and −25.98 mRy/atom (−34.1 kJ/mole, YNi5). The YFe5 compound as well as the SmFe5 compound do not exist in the equilibrium Y—Fe and Sm—Fe phase diagrams, correspondingly, thus no experimental information about the heat of formation of these hypothetical compounds is available. However, the EMTO calculations show that the heat of formation of the YFe5 compound is positive, +6.46 mRy/atom, and is half of the calculated heat of formation of the SmFe5 compound, +12.68 mRy/atom. As a result, the calculated heat of formation of the YFe3Co2 compound, +0.09 mRy/atom, appears to be smaller than the calculated heat of formation of the SmFe3Co2 compound, +2.15 mRy/atom. The computed heats of formation of the YFe3Ni2 and the SmFe3Ni2 compounds are both negative (stable compounds), however, the absolute value of the calculated heat of formation of the YFe3Ni2 compound, |−6.20| mRy/atom, is more than twice as high as the absolute value of the heat of formation of the SmFe3Ni2 compound, |−2.72| mRy/atom. As a result, the region of stability of the pseudo-binary YFe3(Ni1-xCox)2 alloys appears to be almost twice as wide as the region of stability of the pseudo-binary SmFe3(Ni1-xCox)2 alloys.
Y and Co spins align in an antiparallel fashion (AF) that is predicted in the present self-consistent calculations. The calculated total moment, m(tot)=7.82μB/f.u., is slightly smaller than the experimentally reported value of 8.30μB/f.u. The calculated spin moments are 1.55μB and 1.47μB for 2c 104 and 3g 106 sites, correspondingly, which are larger than the recorded experimental values of 1.44μB and 1.31μB. The calculated orbital moments are 0.14μB and 0.11μB for 2c 104 and 3g 106 sites, correspondingly, which are smaller than recorded experimental data of 0.26μB and 0.24μB. The present FREMTO calculations reflect the experimental (spin flip-neuron scattering) observation; for the YCo5 compound, the orbital moment of Co1(2c) 104 atoms is bigger than the orbital moment of Co2(3g) 106 atoms. The large MAE of the YCo5 compound comes from a big orbital allowance from Co1(2c) 104 sites, which are located in the same plane as Y1(1a) 102 sites. Appropriately, Co1(2c) 104 atoms have a big positive MAE allowance, while Co2(3g) 106 atoms have a small negative MAE allowance. The axial (positive) MAE of the YCo5 magnet can be achieved only if orbital moments on the Co1(2c) 104 atoms are bigger than the orbital moments of the Co2(3g) 106 atoms.
A mean-field treatment for the Curie temperature, Tc, can be formulated as:
where
is the difference among the ground state total energies of the DLM and the AF state, and kB is the Boltzmann constant. Principally, an assessment of the Curie temperature can be achieved from the total energy difference between the ferromagnetic (or antiferromagnetic) and the paramagnetic states. The difference between the total energies can be substituted by the difference between the effective single-particle (one atomic specie) energies, which are directly associated with AF and DLM states (the so-called mean-field treatment). In the present work, EtotDLM and EtotAF are calculated at the equilibrium volumes for DLM and AF states, correspondingly. According to the present EMTO-DLM and EMTO-AF calculations, Tc=891.8 K for the YCo5 magnet, which is in good accord with the experimental data Tc=920 K, which is relatively larger than that of the commonly used Nd2Fe14B magnet (Tc=588 K). Similar EMTO calculations reveal Tc=1149.3 K for the YFe5 compound, although this compound does not exist in the Y—Fe phase diagram. There is an experimentally observed tendency of the Curie temperature to increase with Fe doping of the YCo5 magnet, i.e., from Tc=930 K (the YCo5 compound) to Tc=1020 K (the Y(Co0.8Fe0.2)5 compound).
According to the present calculations, the YFe3(Ni0.3Co0.7)2 magnet shows an enormous total moment of m(tot)˜9.79μB, essentially due to the iron atoms that each contribute with 2.45μB. The total moment of the YFe3(Ni0.3Co0.7)2 magnet is thus essentially bigger than that of the traditional YCo5 magnet that has a calculated total moment of m(tot)˜7.82μB. The experimental values of saturation magnetization (Ms) and the maximum energy product ((BH)max) for the YCo5 magnet are 0.85 MA/m and 224 kJ/m3, correspondingly. Because saturation magnetization and magnetic moment are approximately proportional, Ms˜ m(tot), and the maximum energy product is approximately proportional to the square of the saturation magnetization, (BH)max˜(Ms)2, one can evaluate that saturation magnetization for the YFe3(Ni0.3Co0.7)2 magnet is proportional to 1.064 MA/m and the maximum energy product for the YFe3(Ni0.3Co0.7)2 magnet should be approximately 351 kJ/m3, which is ˜69% of the record maximum energy product of the Nd2Fe14B magnet, (BH)max=512 kJ/m3. Particularly, the YFe3(Ni0.3Co0.7)2 magnet, which has a Curie temperature similar to the YCo5 magnet, is a substantially steadier magnet than the YCo5 magnet (its maximum energy product should be ˜57% larger).
The magnetic anisotropy energy (MAE) is one of the more important properties of an efficient magnet. In the quest to increase the saturation magnetic moment or energy product, by substituting cobalt for iron, the impact of the doping on the MAE is reviewed.
For the YFe3Co2 and the YFe3CoNi magnets, the iron atoms are kept on the energetically favorably 3g 106 sites. In the case of YFe3CoNi, Co and Ni are modeled as on the 2c 104 sites as two average atoms consistent with modeling of SmFe3CoNi. In all calculations, the atomic volume is relaxed and the c/a axial ratio of the hexagonal phase. Some sensitivity is found (not shown) of the MAE to the axial ratios, suggesting that the structural relaxation is important.
According to the values calculated in Table 2, both YFe5 and YNi5 have relatively small magnetic anisotropy and, for that reason alone, they are not particularly strong magnets. YFe5 is included in the table to provide context to the other magnets, as it does not exist in the hexagonal phase. YCo5 contrarily exists and is predicted to have significant magnetic anisotropy. DFT-GGA calculations are relied on for these magnetic compounds because GGA performs better for the magnetic 3d transition metals relative to the LDA or even more modern approximations. GGA reproduces the proper magnetic ground state of iron, as opposed to the LDA. The GGA calculations reproduce the experimental atomic volume very well but overestimate the MAE for YCo5 relative to experimental data. DFT-GGA (T=0 K) gives the unit cell volume Vcell=82.65 Å3 and anisotropy K1=9.89 meV/cell (19.2 MJ/m3). These numbers are compared to experimental data at T=4.1 K, Vcell=82.50 Å3, K1=3.80 meV/cell (7.38 MJ/m3) and at T=293 K, Vcell=83.99 Å3, K1=3.04 meV/cell (5.80 MJ/m3). Here, the unit cell volume at T=4.1 K, Vcell=82.50 Å3 is identified using the experimental value of the MAE coefficient, K1, presented in the units of (MJ/m3), and (meV/cell).
Replacing most of Co with Fe in the YCo5 magnet and using Ni as a thermodynamic mediator results in an YFe3CoNi magnet with desired magnetic properties such as a very high Curie temperature, robust magnetic anisotropy, and a relatively large maximum energy product. YFe3CoNi magnets use nickel metal as the stabilizing material in the YCo5 magnet in order to accommodate the maximum amount of iron metal to favor a very high magnetization.
For YFe3(Ni1-xCox)2 alloys, it is possible to have stable solutions until approximately all Ni atoms are substituted by Co atoms. The ab initio heat of formation predictions are confirmed by CALPHAD modeling at 298 K. The combination of negative heat of formation and extended solubility limits experimentally observed in the YTM5 (TM=Co, Fe, Ni) magnets (e.g., complete solubility from YCo5 to YNi5 at 1073 K and 1273 K; solubility of ˜20 at. % Fe in Y(Co,Fe)5 at 1323 K; solubility of ˜30 at. % Fe in Y(Fe,Ni)5 at 873 K) is promising for synthesis of the foregoing magnets. A specific example includes a YFe3Co2 magnet for which the calculated the Curie temperature, Tc, which is equal to 1097.7 K and the maximum energy product, (BH)max(YFe3Co2), as ˜365 kJ/m3, which is ˜71% of the record maximum energy product of the Nd2Fe14B magnet, (BH)max=512 kJ/m3. Here, the maximum energy products of YFe3Co2 and YFe3CoNi magnets are estimated using the calculated total magnetic moments of YFe3Co2, YFe3CoNi, and YCo5 magnets as well as the experimental values of the saturated magnetization and the maximum energy product of the YCo5 magnet. Calculations are performed in the same fashion as for the YFe3(Ni0.3Co0.7)2 magnet.
According to the presently disclosed calculations, the YFe3(Ni0.3Co0.7)2 magnet has a Curie temperature Tc˜900 K that is relatively close to the calculated Curie temperature of the YCo5 magnet, Tc˜ 892 K. In addition, the maximum energy product of the YFe3(Ni0.3Co0.7)2 magnet is significantly improved compared to the YCo5 magnet (˜57% larger). The calculated intrinsic properties of the magnets are reported in Table 3 in conjunction with the experimental data of Nd2Fe14B, SmCo5, and YCo5 magnets for comparison. All four suggested permanent magnets have a Curie temperature significantly higher than that of Nd2Fe14B, Tc˜ 588 K, spanning from 785 K to 1103 K. In addition, their maximum energy products are significantly higher than that of the commercially used SmCo5 and YCo5 magnets (231 kJ/m3 and 224 kJ/m3, respectively), reaching a maximum value of 365 kJ/m3 for YFe3Co2. Our calculated (Table 3, LDA) MAEs for YFe3CoNi magnet is not much smaller than that of YCo5 magnet (10.6 MJ/m3 and 13.5 MJ/m3, respectively).
In Use
Considering SmFe3CoNi and YFe3CoNi magnets comprise up to 80% less Co than their SmCo5 and YCo5 precursors, maturing of these magnets becomes even more captivating from the current economic viewpoint. Replacing part of cobalt with iron in SmCo5 and YCo5 magnets stabilized with a small portion of nickel results in permanent magnets having many desirable characteristics. These permanent magnets are anticipated to have outstanding magnetic properties, a large maximum energy product, a strong magnetic anisotropy, and an exceptionally high Curie temperature.
In use, the alloy formulations described herein may be useful as permanent magnets with high MAE and energy product, and useful for high-temperature applications (e.g., Curie temperatures in a range of about 900 K to about 1100 K). The YCoNiFe3 and SmCoNiFe3 alloy formulations described herein may be used for cost-effective clean energy products, turbines, electric car battery applications, etc.
The inventive concepts disclosed herein have been presented by way of example to illustrate the myriad features thereof in a plurality of illustrative scenarios, embodiments, and/or implementations. It should be appreciated that the concepts generally disclosed are to be considered as modular, and may be implemented in any combination, permutation, or synthesis thereof. In addition, any modification, alteration, or equivalent of the presently disclosed features, functions, and concepts that would be appreciated by a person having ordinary skill in the art upon reading the instant descriptions should also be considered within the scope of this disclosure.
While various embodiments have been described above, it should be understood that they have been presented by way of example only, and not limitation. Thus, the breadth and scope of an embodiment of the present invention should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.
This application is a Continuation in Part of U.S. Non-Provisional patent application Ser. No. 16/478,807 filed Jul. 17, 2019, which is a National Stage Entry of PCT/US2018/014040 filed Jan. 17, 2018, that claims priority to U.S. Provisional Application No. 62/447,373 filed Jan. 17, 2017, all of which are herein incorporated by reference.
This invention was made with Government support under Contract No. DE-AC52-07NA27344 awarded by the United States Department of Energy. The Government has certain rights in the invention.
Number | Name | Date | Kind |
---|---|---|---|
4378258 | Clark et al. | Mar 1983 | A |
20040244876 | Konishi et al. | Dec 2004 | A1 |
20200318222 | Landa et al. | Oct 2020 | A1 |
Number | Date | Country |
---|---|---|
918045 | Jan 1973 | CA |
Entry |
---|
Non-Final Office Action from U.S. Appl. No. 16/478,807, dated Oct. 8, 2021. |
Grace Period Disclosure, “Thermodynamics and Magnetism of YCo5 Compound Doped with Fe and Ni: An Ab Initio Study,” Alexander Landa, Per Söderlind, Emily E. Moore, Aurelien Perron, Aug. 31, 2020, 21 pages. |
Soderlind et al., “Prediction of the new efficient permanent magnet SmCoNiFe3,” Physical Review B 96, 2017, pp. 100401-1-100401-5. |
Landa et al., “Thermodynamics of SmCo5 compound doped with Fe and Ni: An ab initio study,” Journal of Alloys and Compounds, vol. 765, 2018, pp. 659-663. |
Landa et al., “Thermodynamics and Magnetism of YCo5 Compound Doped with Fe and Ni: An Ab Initio Study,” Applied Sciences, vol. 10, 2020, pp. 1-21. |
Gavrikov et al., “Effect of Ni doping on stabilization of Sm(Co1?xFex)5 compound: thermodynamic calculation and experiment,” Journal of Physics: Condensed Matter, vol. 32, 2020, pp. 1-7. |
Coey, J.D.M., “Magnetic Materials for Green Innovation,” Presentation, TMS San Diego, 2014, 50 pages. |
Coey, J.D.M., “Hard Magnetic Materials: A Perspective,” IEEE Transactions on Magnetics, vol. 47, No. 12, Dec. 2011, pp. 4671-4681. |
Coey, J.D.M., “Permanent magnets: Plugging the gap,” Scripta Materialia, vol. 67, 2012, pp. 524-539. |
Paige et al., “The Magnetocrystalline Anisotropy of Cobalt,” Journal of Magnetism and Magnetic Materials, vol. 44, 1984, pp. 239-248. |
Ermolenko et al., “Giant coercive force and certain features in the magnetization reversal of bulky single crystals of the intermetallic compounds Sm(C01-xNix)s,” JETP Letters, vol. 21, No. 1, Jan. 5, 1075, 2 pages. |
Liu et al., “Handbook of Advanced Magnetic Materials, vol. I: Advanced Magnetic Materials: Nanostructural Effects” Springer Science+Business Media, Inc., 2006, 47 pages. |
Coey, J.D.M., “Magnetism and Magnetic Materials,” Cambridge University Press, 2009, 633 pages. |
Miyazaki et al., “Formation and Magnetic Properties of Metastable (TM)5Sm and (TM)7Sm2 (TM=Fe,Co) Compounds,” Journal of Magnetism and Magnetic Materials, vol. 75, 1988, pp. 123-129. |
Miyazaki et al., “Formation of metastable compounds and magnetic properties in rapidly quenched (Fe1?x Cox)5Sm and (Fe1?xCox)7Sm2 alloy systems,” Journal of Applied Physics, vol. 64, No. 10, Nov. 15, 1988, pp. 5974-5976. |
Larson et al., “Calculation of magnetic anisotropy energy in SmCo5,” Physical Review B, vol. 67, 2003, pp. 214405-1-214405-6. |
Laforest et al., “Neutron Diffraction Study of the Th (Co1-xFex)5 Alloys,” IEEE Transactions on Magnetics, Sep. 1973, pp. 217-220. |
Liu et al., “Magnetic moments and exchange interaction in Sm(Co,Fe)5 from first-principles, Computational Materials Science,” Computational Materials Science, vol. 50, 2011, pp. 841-846. |
Guo et al., “Standard Enthalpies of Formation for some Samarium Alloys, Sm+Me (Me=Ni, Rh, Pd, Pt), Determined by High-Temperature Direct Synthesis Calorimetry,” Metallurgical and Materials Transactions B, vol. 29B, Aug. 1998, pp. 815-820. |
Liu et al., “Effect of Fe partial substitution for Co on the magnetic properties of Y(Co,Fe)5 from first-principles,” Journal of Applied Physics, vol. 107, 2010, pp. 09A718-1-09A718-3. |
Meyer-Liautaud et al., “Enthalpies of Formation of Sm—Co Alloys in the Composition Range 10-22 at. %Sm,” Journal of the Less-Common Metals, vol. 127, 1987, pp. 243-250. |
Rosner et al., “Magneto-elastic lattice collapse in YCo5,” Nature Physics Letters, vol. 2, Jul. 2006, pp. 469-472. |
Nouri et al., “The isothermal section phase diagram of the Sm—Fe—Ni ternary system at 800° C.,” Journal of Alloys and Compounds, vol. 661, 2016, pp. 508-515. |
Tie-Song et al., “Magnetic properties of R ions in RCo5 compounds (R=Pr, Nd, Sm, Gd, Tb, Dy, Ho, and Er),” Physical Review B, vol. 43, No. 10, Apr. 1, 1991, pp. 8593-8598. |
Streever, R.L., “Individual Co site contributions to the magnetic anisotropy of RCo5 compounds and related structures,” Physical Review B, vol. 19, No. 5, Mar. 1, 1979, pp. 2704-2711. |
Givord et al., “Temperature dependence of the samarium magnetic form factor in SmCo5,” Journal of Applied Physics, vol. 50, No. 3, Mar. 1979, pp. 2008-2010. |
Heidemann et al., “Investigation of the Hyperfine Fields in the Compounds LaCo13, LaCo5, YCo5 and ThCo5 by Means of Inelastic Neutron Scattering,” Z. Physik B, vol. 22, 1975, pp. 367-372. |
Alameda et al., “Large Magnetization Anistrophy in Uniaxial YCo5 Intermetallic,” Journal of Magnetism and Magnetic Materials, 1980, pp. 1257-1258. |
Schweizer et al., “Polarised neutron study of the RCo5 intermetallic compounds. I. The cobalt magnetisation in YCo5,” Journal of Physics F: Metal Physics, vol. 10, 1980, pp. 2799-2817. |
Niarchos, D., “‘Artificial Multi-Elements’ based on High Entropy Alloys as ‘building blocks’ for novel magnetic alloys suitable for Permanent Magnets: Special cases ThMn12 and SmFe3CoNi,” The European Conference Physics of Magnetism (PM'21), 2021, 2 pages, retrieved from https://www.ifmpan.poznan.pl/pm21/invited-speakers.html. |
International Search Report and Written Opinion from PCT Application No. PCT/US2018/014040, dated Mar. 26, 2018. |
Landa et al., “Thermodynamics of the Doped Sm(Co1-XFeX)5 Alloys: Ab Initio Study,” AVS 63rd International Symposium & Exhibition, May 9, 2016, 2 pages (abstract only). |
Miyazaki et al., “Formation of Compounds and Their Magnetic Properties of Rapidly Quenched (Fe1-x Cox)4.5(Ni,Al) 0.5 Sm Alloys,” IEEE Translation Journal on Magnetics in Japan, vol. 6, No. 10, Oct. 1991, pp. 908-913. |
Lamichanne et al., “Magnetic Properties Hard-Soft SmCo5—FeNi and SmCo5—FeCo Composites Prepared by Electroless Coating Technique,” Open Journal of Composite Materials, No. 2, Oct. 2012, pp. 119-124. |
Laforest et al., “Neutron Diffraction Study of the Th (col-xFex)5 Alloys,” IEEE Transactions on Magnetics, vol. MAG-9, No. 3, Sep. 1973, pp. 217-220. |
Nouri et al., “The isothermal section phase diagram of the Sm—Fe—Ni ternary system at 800 oC,” Journal of Alloys and Compounds vol. 661, 2016, pp. 508-515. |
Liu et al., “Magnetic moments and exchange interaction in Sm(Co,Fe)5 from first-principles,” Computational Materials Science, vol. 50, 2011, pp. 841-846. |
International Preliminary Examination Report from PCT Application No. PCT/US2018/014040, dated Aug. 1, 2019. |
Landa et al., U.S. Appl. No. 16/478,807, filed Jul. 17, 2019. |
Turchi et al., “Ab initio-aided Thermodynamics of Rare Earth-based Alloys,” Abstracts of MS&T, Oct. 2016, 2 pages (abstract only). |
Landa et al., “Thermodynamics of Sm(Co1-xFex)5 Alloys Doped with Ni: Ab Initio Study: Project 2.1.6,” Presentation from Critical Materials Institute 4th Annual Meeting (CMI), Aug. 18, 2016, 17 pages. |
Landa et al., “Thermodynamics of Sm(Co1-xFex)5 Alloys Doped with Ni: Ab Initio Study,” AVS 63nd International Symposium & Exhibition, Presentation, Nov. 6-11, 2016, 24 pages. |
Landa et al., “Thermodynamics of the SmCo5 Compound Doped with Fe and Ni: An AB Initio Study,” arXiv, Lawrence ivermore National Laboratory, Dec. 13, 2016, 23 pages, retrieved from https://arxiv.org/abs/1707.09447. |
Soderlind et al., “Prediction of the new efficient permanent magnet SmCoNiFe3,” Americal Physical Society, Physical Review B, vol. 96, 2017, pp. 100404:1-100404:5. |
Perron et al., “Impact of MDS on materials design Update on hard magnet studies,” Lawrence Livermore National aboratory, Presented at CMI Annual Meeting, Aug. 29-31, 2017, 1 page, retrieved from https://cmi.ameslab.gov/2017-annual-meeting. |
Daene et al., “Study of 1:5-Type Rare Earth Magnets and Compounds,” Critical Materials Institute, Presented at CMI Annual Meeting, Aug. 29-31, 2017, 1 page, retrieved from https://cmi.ameslab.gov/2017-annual-meeting. |
Landa et al., “Thermodynamics of the SmCo5 and Magnet Doped with Fe and Ni: AB Initio Study,” Euromat, Jan. 19, 2017, 2 pages, (abstract only). |
Landa et al., “Thermodynamics of SmCo5 Magnet Doped with Fe and Ni: Ab Initio Study,” Lawrence Livermore National Laboratory, Presentation from European Congress and Exhibition on Advanced Materials and Processes (EUROMAT), Sep. 17-22, 2017, 20 pages. |
Landa et al., “Thermodynamics of SmCo5 compound doped with Fe and Ni: An ab initio study,” Journal of Alloys and Compounds, vol. 765, Jun. 23, 2018, pp. 659-663. |
Turchi et al., “Application of Thermodynamics to Rare Earth-Based Alloy Design,” TMS 146th Annual Meeting and Exhibition, Jul. 29, 2016, 2 pages (abstract only). |
Turchi et al., “Efficient Prototyping of Rare Earth-based Alloys from Ab Initio Electronic Structure and Thermodynamics: Ab Initio-aided Thermodynamics of Complex Multi-component Alloys,” Critical Materials Institute, Presentation, Aug. 16-18, 2016, 12 pages. |
Final Office Action from U.S. Appl. No. 16/478,807, dated Feb. 10, 2022. |
Turchi et al., “Ab Initio-aided Thermodynamics of Rare Earth-based Alloys,” MS&T '16, Presentation, Oct. 23-27, 2016, pp. 1-44. |
Turchi et al., “Advanced Theoretical Screening of Multi-component Alloys,” Japan-US Bilateral 4th Meeting on Rare Metals, Presentation, Nov. 7, 2016, pp. 1-17. |
Niarchos et al., “Artificial Multi-Elements”based on High Entropy Alloys as “building blocks” for novel magnetic alloys suitable for Permanent Magnets: Special cases ThMn12 and SmFe3CoNi, “abstract presented at the European Conference” Physics of Magnetism 2021 (PM '21), Poznan, Poland, Jun. 28-Jul. 2, 2021, 2 pages. |
Restriction Requirement from U.S. Appl. No. 16/478,807, dated Jun. 29, 2021. |
Examiner's Answer to Appeal Brief from U.S. Appl. No. 16/478,807, dated Sep. 22, 2022. |
Number | Date | Country | |
---|---|---|---|
20210375511 A1 | Dec 2021 | US |
Number | Date | Country | |
---|---|---|---|
62447373 | Jan 2017 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 16478807 | US | |
Child | 17398905 | US |