Patent Application
20130038160
The present invention is directed to mechanically strong, sequentially laminated, rare earth, permanent magnets having sulfide-based dielectric layers separated from permanent magnet layers by transition and/or diffusion reaction layers.
The present invention relates to sequentially laminated, rare earth, permanent magnets for use in high performance, rotating machines. The high electrical resistivity, rare earth, permanent magnets of the invention, with sulfide-based dielectric layers; are characterized by reduced eddy current losses combined with improved mechanical properties suitable for use in high performance, rotating machines. Rare earth, permanent magnets of the invention featuring sulfide-based dielectric layer(s), combined with improved mechanical properties, are particularly well suited for commercial use in high performance, rotating machines, such as motors and generators.
Addressing eddy current losses in permanent magnets is critical in the design of high performance motors and high speed generators. Reduction of these eddy current losses in permanent magnets used with rotating machines is preferably accomplished by increasing the electrical resistivity of the permanent magnets. For example, when rare earth permanent, magnets are subjected to variable magnetic flux, and the electrical resistivity is low, excessive heat attributed to an eddy current is generated. This increased heat reduces the magnetic properties of the permanent magnet with corresponding reductions in the efficiency of rotating machines.
Adding layers of high resistivity, dielectric material to laminated, rare earth magnets, perpendicular to the plane of the eddy currents, generally results in a substantial decrease of eddy current losses. However, heretofore adding these layers of high resistivity material to laminated, permanent magnets were generally associated with shortcomings in mechanical properties. Specifically, these composite, laminated, permanent magnets with improved electrical resistivity failed in commercial use in high performance, rotating machines due to shortcomings in mechanical properties. Demands of high performance, rotating machines require improved mechanical properties beyond those traditionally available in laminates with suitable dielectric properties.
Rare earth, permanent magnets with improved electrical resistivity are described in U.S. Patent Publication No. US2006/0292395 A1 and U.S. Pat. Nos. 5,935,722; 7,488,395 B2; 5,300,317; 5,679,473; 5,763,085 and in U.S. patent application, “Rare Earth Laminated Composite Magnets with Increased Electrical Resistivity; and Ser. No. 12/707,227 filed Feb. 17, 2010.
U.S. Patent Publication No. 2006/0292395 A1 teaches fabrication of rare earth magnets with high strength and high electrical resistance. The structure includes R—Fe—B-based rare earth magnet particles which are enclosed with a high strength and high electrical resistance composite layer consisting of a glass phase or R oxide particles dispersed in a glass phase, and R oxide particle based mixture layers (R=rare earth elements).
U.S. Pat. No. 5,935,722 teaches the fabrication of laminated composite structures of alternating metal powder layers, and layers formed of an inorganic bonding media consisting of ceramic, glass, and glass-ceramic layers which are sintered together. The ceramic, glass, and glass-ceramic layers serve as an electrical insulation material used to minimized eddy current losses, as well as an agent that bonds the metal powder layers into a dimensionally-stable body.
U.S. Pat. No. 7,488,395 teaches fabrication of a functionally graded rare earth permanent magnets having a reduced eddy current loss. The magnets are based on R—Fe—B (R=rare earth elements) and the method consists in immersing the sintered magnet body into a slurry of powders containing fluorine and at least one element E selected from alkaline earth metal elements and rare earth elements, mixed with ethanol. Subsequent heat treatment of the magnets covered with the respective slurry allows for the absorption and infiltration of fluorine and element E from the surface into the body of the magnet. Thus, the magnet body includes a surface layer having a higher electric resistance than the interior.
U.S. application Ser. No. 12/707,227, teaches laminated, composite, rare earth magnets with improved electrical resistivity.
To date, there is no teaching implied nor suggested in the prior art of the critical elements of the present invention including:
A. “Intermediate” transition and/or diffusion reaction layers, combined with sequentially laminated layers of permanent magnets based on Sm—Co or Nd—Fe—B, where the transition and/or diffusion reaction layers surround and separate a sulfide-based, dielectric layer(s) from permanent magnet layers. The sequentially laminated, rare earth, permanent magnets of the present invention comprise Sm—Co or Nd—Fe—B layers separated from sulfide-based, dielectric layers by transition and/or diffusion reaction layers. All the layers in the sequentially laminated, rare earth, permanent magnet are consolidated simultaneously with the sequentially laminated, permanent magnet indicating acceptable magnetic properties with improved mechanical strength sufficient to support use with high performance, high speed rotating machines.
B. Monolithic, sequentially laminated structures consisting of sequential layers of rare earth based magnets and layers of sulfide-based dielectric materials separated from the permanent magnet layers by transition and/or diffusion reaction layers. These sulfide-based, dielectric layers provide unexpected advantages in electrical resistivity as the laminated, dielectric layers partly interact at the interface, creating a transition and/or diffusion reaction layer separating the dielectric layer from the permanent magnet layer. The resultant sequentially laminated, rare earth, permanent magnet exhibits exceptional electrical resistivity combined with no compromise in magnetic properties and improved mechanical strength.
There is no teaching in the prior art of “intermediate”, “transition”, and/or “diffusion reaction” layers separating laminated layers of rare earth, permanent magnet materials based on Sm—Co or Nd—Fe—B from layers of sulfide-based, dielectric materials selected from S or mixtures of sulfide and fluoride.
For purposes of the present invention, sulfide-based dielectrics include: Al2S3, Sb2S3, As2S3, BaS, BeS, Bi2S3, B2S3, CdS, CaS, CeS, Ce2S3, WS, Cr2S3, CoS, CoS2, Cu2S, CuS, Dy2S3, Er2S3, EuS, Gd2S3, Ga2S3, GeS, GeS2, HfS2, Ho2S3, In2S, InS, FeS, FeS2, La2S3, LaS2, La2O2S, PbS, Li2S, MgS, MnS, HgS, MoS2, Nd2S3, NiS, NdS, K2S, Pr2S3, Sm2S3, Sc2S3, SiS2, Ag2S, Na2S, SrS, Tb2S, Tl2S, ThS2, Tm2S3, SnS, SnS2, TlS2, WS2, US2, V2S3, Yb2S3, Y2S3, Y2S3, Y2O2S, ZnS and ZrS2 or a combination of any of these materials.
For purposes of the present invention, sulfide-based, dielectric materials include the sulfide compounds described above and:
Oxysulfides,
Sulfides and oxyfluorides,
Mixtures of sulfides,
Mixtures of sulfides and fluorides,
Mixtures of sulfides, fluorides, oxysulfides and/or oxyfluorides, and/or
Each of the above mixed with rare earth alloys.
A primary object of the invention is to produce mechanically strong, high electrical resistivity, Sm—Co and Nd—Fe—B, sequentially laminated, rare earth, permanent magnets with sulfide-based, dielectric layers separated from the rare earth, permanent magnet layers by transition and/or diffusion reaction layers.
Another object of the invention is to produce the first sequentially laminated, Sm—Co and Nd—Fe—B magnets capable of delivering high electrical resistivity without sacrificing mechanical strength or magnetic properties.
An object of the present invention is to form sequentially laminated structures with increased electrical resistivity consisting of sequential layers of rare earth, permanent magnet and sulfide-based, dielectric layers, which are separated from the permanent magnet layers by transition and/or diffusion reaction layers, where the sequentially laminated magnets are suitable for reducing eddy current losses without sacrificing rare earth, permanent magnet properties and with mechanical strength suitable for use in high performance motors and generators.
Another object of the invention is to form sequentially laminated structures with increased electrical resistivity consisting of sequential layers of rare earth, permanent magnets separated from layers of mixtures of sulfide-based, dielectric materials and rare earth rich alloys separated from the permanent magnet layers by transition and/or diffusion reaction layers; where the sequential laminate is suitable for reducing eddy current losses when used in high performance motors and generators, while maintaining a mechanically strong laminate structure without sacrificing magnetic properties.
A further object of the invention is to form sequentially laminated structures with increased electrical resistivity consisting of sequential layers of (1) sulfide-based dielectric layers, (2) transition and/or diffusion reaction, rare earth, rich alloy layers surrounding the dielectric layers, and (3) rare earth, permanent magnet layers suitable for reducing eddy current losses when used in high performance motors and generators, while indicating improved mechanical strength over traditional, sequentially laminated, rare earth, permanent magnets.
Still a further object of the invention is to form sequentially laminated structures with increased electrical resistivity consisting of: sequential layers of sulfide-based dielectric materials; transition and/or diffusion reaction layers and rare earth, permanent magnet layers, where the sequentially laminated, permanent magnet is suitable for reducing eddy current losses when used in high performance motors and generators.
Another object of the invention is to form mechanically strong, sequentially laminated structures with increased electrical resistivity consisting of layers of sulfide dielectric materials surrounded by transition and/or diffusion reaction layers and layers of rare earth, permanent magnet materials sequentially laminated, suitable for reducing eddy current losses when used in high performance motors and generators.
Another object of the invention is to form mechanically strong, sequentially laminated structures with increased electrical resistivity consisting of layers of dielectric layer made of sulfide and fluoride mixtures surrounded by transition and/or diffusion reaction layers and layers of rare earth, permanent magnet materials sequentially laminated, suitable for reducing eddy current losses when used in high performance motors and generators.
Yet another object of the invention is to form sequentially laminated, rare earth, permanent magnet structures with increased electrical resistivity with mechanical strength suitable for use in high performance, rotating machines.
The above and other objects, features and advantages of the present invention will be better understood from the following detailed description of the invention taken in conjunction with accompanying
The following terms are defined as set out below, to insure a clear understanding of the invention and its unexpected resistivity/mechanical properties as detailed in the Examples, Drawings and Tables, as set forth below and in the claims.
“Rare earth permanent magnets” are defined as permanent magnets based on intermetallic compounds with rare earth elements, RE, such as Nd and Sm, transition metals, such as Fe and Co, and, optional, metalloids such as B. Other elements may be added to improve magnetic properties.
“Sequentially laminated structures” are defined as structures containing at least two permanent magnet layers separated from one dielectric layer by at least two transition and/or diffusion reaction layers.
“Eddy current” is defined as the vortex currents generated in electrically conductive materials when exposed to variable magnetic fields. Eddy currents result in building up heat which adversely affects the magnetic properties of permanent magnets.
“Electrical resistivity” is defined as a measure of the resistance strength by which a material opposes the flow of electric current.
“Dielectric” is defined as a material exhibiting high electrical resistivity exceeding 1MΩ.
“High electrical resistivity layer” is defined as a sulfide-based, laminate layer of material with electrical resistivity greater than that of surrounding transition and/or diffusion reaction layers and the rare earth, permanent magnet layers.
“Transition layer” is here defined as a layer introduced into a sequentially laminated, permanent magnet where the transition layer properties compensate for alteration of the stoichiometry at the interface between two distinct crystallographic layers having diverse compositions and diverse functions (i.e., a dielectric function and a magnet function).
“Diffusion reaction layers” are defined as layers in sequentially laminated, permanent magnets of the invention that surround sulfide-based dielectric layers physically separating the permanent magnet layers from sulfide-based, dielectric layers.
“Rare earth rich alloy” is defined as an alloy containing one or more rare earth element(s) in an amount exceeding specific phase stoichiometries.
“Green compact” defines a permanent magnet composite which is consolidated by pressing the precursor powders at room temperature, resulting in a density less than that of the bulk (with no porosity) counterpart.
“Elemental diffusion” is defined as the diffusion or migration of atomic species in the transition and/or diffusion reaction layer due to thermal activation.
“Diffusion reaction interface layer” is here defined as that region between the permanent magnet layers and the dielectric layers, where the original stoichiometry is altered due to the diffusion of the atomic species and their eventual reaction.
“Sulfide-based dielectric material” is defined as sulfides, oxysulfides, sulfide and oxyfluoride mixtures, mixtures of sulfides and fluorides and mixtures of sulfides, fluorides, oxysulfides and/or oxyfluorides and where each of the above can be mixed with rare earth alloys.
“Sequentially laminated permanent magnets with sulfide-based dielectric layers” are defined as monolithic, sequentially laminated structures consisting of sequential layers of rare earth-based magnets, transition and/or diffusion reaction layers surrounding sulfide-based dielectric layers.
“Mechanically strong, sequentially laminated, rare earth, permanent magnets with enhanced electrical resistivity” are defined as magnets of the invention which exhibit mechanical strength:
An accepted approach to minimizing eddy current losses that plague rare earth permanent magnets used in high performance, electric motors or other rotating machines is to machine rare earth permanent magnets into segments which are subsequently assembled into the desired configuration or to alternatively blend the magnet powder precursor with an electrical insulating material.
The present invention provides for an improved rare earth, permanent magnets with minimum eddy current losses; comprising forming monolithic laminated structures consisting of sequential (1) layers of rare earth magnets, (2) layers of sulfide-based dielectrics and/or layers of mixtures of rare earth rich alloys and sulfide-based dielectric materials, separated by (3) transition and/or diffusion reaction layers.
This sequential laminating process of the invention results in transition and/or diffusion reaction layers separating the sulfide-based dielectric layer from rare earth, permanent magnet layers as shown in
The function of the transition and/or diffusion reaction layers is to compensate for an interaction that occurs between the sulfide-based dielectric layer and the rare earth magnet layer. This interaction modifies the stoichiometry at the rare earth, permanent magnet/dielectric interface. The resulting transition and/or diffusion reaction layer accommodates variances in diffusion reactions between the dielectric layer and the various permanent magnet layers or permanent magnet alloy layers comprising the rare earth, permanent magnet layers.
It is suggested that the transition and/or diffusion reaction layer surrounding the sulfide-based dielectric layer plays a key role in the improved mechanical strength of the sequentially laminated, permanent magnets of the invention.
The laminated, permanent magnets of the present invention comprise sequential layers whose compositions interact at the interface with the dielectric layer. Laminated permanent magnets of the invention, as detailed in Examples 1 through 8 and further illustrated in
In a preferred embodiment of the invention, substances for the dielectric layer are selected from the group consisting sulfide-based, dielectric/semiconductor materials, wherein sulfides refers to the group consisting of Al2S3, Sb2S3, As2S3, BaS, BeS, Bi2S3, B2S3, CdS, CaS, CeS, Ce2S3, WS, Cr2S3, COS, CoS2, Cu2S, CuS, Dy2S3, Er2S3, EUS, Gd2S3, Ga2S3, GeS, GeS2, HfS2, Ho2S3, In2S, InS, FeS, FeS2, La2S3, LaS2, La2O2S, PbS, Li2S, MgS, MnS, HgS, MoS2, Nd2S3, NiS, NdS, K2S, Pr2S3, Sm2S3, Sc2S3, SiS2, Ag2S, Na2S, SrS, Tb2S, Tl2S, ThS2, Tm2S3, SnS, SnS2, TiS2, WS2, US2, V2S3, Yb2S3, Y2S3, Y2S3, Y2O2S, ZnS, ZrS2 and combinations thereof, as well as combinations of any of these materials with: sulfides, oxysulfides, sulfides and oxyfluorides, mixtures of sulfides; sulfides and fluorides; sulfides, fluorides, oxysulfides and oxyfluorides. In addition, mixtures of all of the above with rare earth alloys can be used as the dielectric layer.
The preferred rare earth permanent magnet materials of the present invention include Sm—Co and Nd—Fe—B based intermetallic compounds, which are described in Examples 1 through 8 and
The distinctive, magnetic properties of the present invention are based on the morphology of sequentially laminated, permanent magnet layers with sulfide-based, dielectric layers where the dielectric layer is accompanied by transition and/or diffusion reaction layers separating dielectric layer(s) from rare earth, permanent magnet layer(s) as shown in
In the sequentially laminated magnets of the present invention, the composition of the rare earth permanent magnet material, particularly the amount of the rare earth component in the laminate, is increased at the interface with the dielectric layer, i.e., at the transition and/or diffusion reaction layer. This can be achieved by capitalizing on different morphologies: (a) by replacing pure dielectric substances with mixtures of dielectric substances with rare earth rich alloys, or (b) by using rare earth, rich alloy, transition and/or diffusion reaction layers between dielectric layers and magnet layers. This elemental diffusion feature of the magnets of the present invention is achieved during thermal processing of the laminate rare earth magnets of the invention, resulting in transition and/or diffusion reaction layers forming at the interface between the Sm-rich magnet layer and the sulfide-based, dielectric layer. This is shown, for example, in
The thickness of the dielectric layer in the sequentially laminated magnet is preferably adjusted between an upper limit determined by bonding strength and a lower limit controlled by continuity of the dielectric layer. In a preferred embodiment of the invention, the thickness of the dielectric layer is normally less than 500 μm. More preferably, the dielectric layer is less than 100 μm thick. The number of dielectric layers in the laminate magnets will be determined by the application of the sequentially laminated, permanent magnet. For example, in cases of high speed machines, more dielectric layers are preferred. The thickness of the rare earth, permanent magnet layers are also determined by the application, and are usually not less that 500 μm.
Consolidation methods of the present invention required to achieve full density of the sequentially laminated, permanent magnet include: sintering, hot pressing, die upsetting, spark plasma sintering, microwave sintering, infrared sintering, combustion driven compaction and combinations thereof. These are referenced in Examples 1 through 8 and in Examples 9 through 17 set forth in Table 2.
Delamination of the magnets of the present invention can be controlled by the thickness of the dielectric layer and the mechanical strength of the sequentially laminated, permanent magnet. The improved mechanical strength of the rare earth, permanent magnets of the invention is determined, in part, by the bonding strength between the transition and/or diffusion reaction layers and the permanent magnet layers. Breakage of the laminated structures during processing is controlled in the present invention by introducing different morphologies into the green compact, for example, into: (1) partial layers near one of the magnetic poles of the magnet, and (2) partial layers in the center of the magnet.
Thus, one embodiment of the invention is a laminated, rare earth, permanent magnet, having improved electrical resistivity, comprising sequential layers of (1) rare earth, permanent magnets and (2) dielectrics layers where each dielectric layer is surrounded by transition and/or diffusion reaction layers that interface with permanent magnet layers.
Another embodiment of the invention is a laminated, rare earth, permanent magnet having improved electrical resistivity, comprising sequential layers of rare earth permanent magnet and dielectric layers surrounded by transition and/or diffusion reaction layers, wherein said rare earth, permanent magnet layers are selected from the group of intermetallic compounds consisting of:
RE(Co,Fe,Cu,Zr)z,
RE-TM-B,
RE2™14B,
RE-Co
RE2Co17,
RECo5 and
Yet another embodiment of the invention is a laminated, rare earth, permanent magnet, having improved electrical resistivity and improved mechanical strength without compromising magnetic properties comprising sequential layers of rare earth, permanent magnet and sulfide-based dielectric layers surrounded by transition and/or diffusion reaction layers and combinations thereof; wherein said dielectric material is sulfide-based and is selected from the group consisting of:
S or S/F-based dielectric/semiconductor materials, wherein sulfides refer to: Al2S3, Sb2S3, As2S3, BaS, BeS, Bi2S3, B2S3, CdS, CaS, CeS, Ce2S3, WS, Cr2S3, CoS, CoS2, Cu2S, CuS, Dy2S3, Er2S3, EuS, Gd2S3, Ga2S3, GeS, GeS2, HfS2, Ho2S3, In2S, InS, FeS, FeS2, La2S3, LaS2, La2O2S, PbS, Li2S, MgS, MnS, HgS, MoS2, Nd2S3, NiS, NdS, K2S, Pr2S3, Sm2S3, Sc2S3, SiS2, Ag2S, Na2S, SrS, Tb2S, Tl2S, ThS2, Tm2S3, SnS, SnS2, TiS2, WS2, US2, V2S3, Yb2S3, Y2S3, Y2S3, Y2O2S, ZnS, ZrS2 and combinations thereof or a combination of any of the foregoing with sulfides, oxysulfides, mixtures of sulfides, mixtures of sulfides with oxyfluorides, mixtures of sulfides and fluorides, mixtures of sulfides, fluorides, oxysulfides and/or mixtures oxyfluorides, and/or combinations of the above with rare earth alloys.
In another embodiment of the invention, a sequentially laminated, rare earth, permanent magnet, as described herein, the thickness of said sulfide-based dielectric layer is less than about 2 mm and more preferably less than 500 μm.
Yet another embodiment of the invention calls for a sequentially laminated, rare earth, permanent magnet as described herein, wherein said rare earth permanent magnet material layer is represented by the chemical formula:
RE11.7+xTM88.3−x−yBy
where x=0 to 5, y=5 to 7; RE is selected from the group consisting of rare earth elements including Nd, Pr, Dy and Tb; and TM is selected from the group consisting of transition metal elements including Fe, Co, Cu, Ga and Al.
Another embodiment of the invention calls for a sequentially laminated, rare earth magnet as described herein, wherein said transition layer consists of rare earth rich alloys represented by the formula:
RE11.7+xTM88.3−x−yBy
where x is from 5 to 80, y is from 0 to 6; RE is selected from the group consisting of rare earth elements including Nd, Pr, Dy and Tb; and TM is selected from the group consisting of transition metal elements including Fe, Co, Cu, Ga and Al.
Yet another embodiment of the invention calls for a sequentially laminated, rare earth, permanent magnet, as described herein, wherein said rare earth, permanent magnet material is represented by the formula:
RE(CouFevCuwZrh)z
wherein u is from about 0.5 to 0.8, v is from about 0.1 to 0.35, w is from about 0.01 to 0.2, h is from about 0.01 to 0.05, and z is from about 6 to 9; and wherein RE is selected from the group consisting of Sm, Gd, Er, Tb, Pr, Dy and combinations thereof.
Another embodiment of the invention calls for a sequentially laminated, rare earth, permanent magnet, as described herein, wherein said rare earth magnet material is represented by the formula:
RECox
where x is from 4 to 6 and RE represents rare earth elements including Sm, Gd, Er, Tb, Pr, and Dy and mixtures thereof, while other metallic or non-metallic elements are optional and should not exceed 10 atomic %.
Yet another embodiment of the invention calls for a sequentially laminated, rare earth permanent magnet as described herein, wherein said transition layer is a rare earth rich alloy having the formula:
RE(CouFevCuwZrh)z
wherein u=0 to 0.8, v=0 to 0.35, w=0 to 0.20, h=0 to 0.05, z=1 to 7; and RE is selected from the group consisting of rare earth elements and mixtures thereof.
Another embodiment of the invention calls for a sequentially laminated, rare earth, permanent magnet as described herein, wherein said transition layer is a rare earth rich alloy having the formula:
RECox
where x is from 1 to 4 and RE is selected from the group consisting of rare earth elements and mixtures thereof.
Yet another embodiment of the invention calls for a sequentially laminated, rare earth, permanent magnet as described herein, wherein said sulfide-based dielectric is selected from the group consisting of:
RE11.7+xTM88.3−x−yBy
where x=5 to 80, y=0 to 6: RE is selected from the group consisting of rare earth elements selected from the group consisting of Nd, Pr, Dy, and Tb; and TM is selected from the group consisting of transition metal elements Fe, Co, Cu, Ga, and Al.
Another embodiment of the invention calls for a sequentially laminated, rare earth, permanent magnet as described herein, wherein said sulfide-based dielectric layer contains at least 30 weight % of said sulfide-based, dielectric material with the balance comprising a rare earth rich alloy having the formula:
RE(CouFevCuwZrh)z
wherein u=0 to 0.8, v=0 to 0.35, w=0 to 0.20, h=0 to 0.05, z=1 to 7; and RE is selected from the group consisting of rare earth elements consisting of Nd, Pr, Dy, and Tb.
Yet another embodiment of the invention calls for a sequentially laminated, rare earth, permanent magnet as described herein, wherein said sulfide-based, dielectric layer comprises at least 30 weight % of said sulfide-based, dielectric material with the balance comprising a rare earth rich alloy having the formula:
RECox
wherein x=1 to 4 and RE represents a rare earth element.
Another embodiment of the invention is directed to improvements in high performance, electric motors and generators having improved mechanical strength and electrical resistivity with no compromise in magnetic properties using rare earth magnets of the invention with reduced eddy current losses comprising sequentially laminated, rare earth, permanent magnet layers and sulfide-based dielectrics surrounded by transition and/or diffusion reaction layers.
Yet another embodiment of the invention is directed to improvements in high-performance, rotating machines by reducing eddy current losses with improved mechanical strength with no compromise in magnetic properties through the use of sequentially laminated, rare earth, permanent magnet layers, separated from sulfide-based, dielectric layers by transition and/or diffusion reaction layers.
Another embodiment of the invention is a sequentially laminated, rare earth, permanent magnet as described herein, wherein the diffusion reaction layers are arranged as shown in
Yet another embodiment of the invention is a sequentially laminated, rare earth, permanent magnet as described herein, wherein said laminated layers are arranged as shown in
Another embodiment of the present invention calls for a sequentially laminated, rare earth, permanent magnet, as described herein, wherein said laminated layers are arranged as shown in
Yet another embodiment of the invention is a sequentially laminated, rare earth, permanent magnet, as described herein, wherein said laminated layers are arranged as shown in
The sequentially laminated, rare earth, permanent magnets of the invention with high electrical resistivity and improved mechanical strength with no compromise in magnetic properties can be produced according to one of the method of manufacture for the present invention by pressing sequential layers as illustrated in
The permanent magnet powder may be prepared by coarsely pulverizing the precursor ingots produced by melting and casting the starting material and pulverizing in a jet mill, ball mill, etc., to particles having an average particle size from 1 to 10 μm, preferably from 3 to 6 μm.
In one process for producing the sequentially laminated magnets of the present invention, submicron sized sulfide and fluoride particles used in the dielectric layers of the sequentially laminated, permanent magnets of the invention are prepared using either top down or bottom up manufacturing. For example, top down approaches include: mechanical milling, ball milling, mechanical alloying, low energy ball milling and high energy ball milling, and combinations thereof. In contrast, bottom up approaches include various chemical approaches followed by annealing.
In the various processes used to manufacture the magnets of the present invention, sulfide-based, dielectric particles suitable for the dielectric laminate of the present invention can be prepared by various methods, including:
1. Homogeneous gas phase reactions with volatile sulfur precursors
2. Gas-Solid reactions
3. Reactions with elemental sulfur
4. Solution Processes
5. Solvated Elemental Sulfur
6. Homogeneous Precipitation
7. Flux driven reactions
8. Reduction Process
9. Thermal decomposition of Dithiolato Complexes
10. Non-Aqueous Solvent Routes using metal alkyls and Sulfur precursors
11. Ceramic Method (High Temperature Solid State Synthesis)
12. Sulfidized Sol-Gel derived Precursors
Dielectric fluoride particles suitable for use in combination with sulfide-based dielectrics, of the present invention, can be prepared using the following methods:
Gas solid reactions
Solution processes
Co-precipitation processes
Ball milling processes
Particle sizes of referenced sulfide-based dielectric particles can be further reduced by a variety of milling techniques and ultrasonic processes.
In the processes used to manufacture the sequentially laminated magnets of the present invention, colloidal or submicron sized sulfide particles are mixed with polar or non-polar solvents at different concentrations based on the density of the dielectric material and the volume required to produce a particular dielectric layer thickness on the green compact pressed magnetic materials layer. The dielectric materials are introduced onto the surface of the pressed green, compact, thick magnetic layers using a semi-automatic, flow rate controlled, sprayer which controls the flow rate of the colloidal dielectric particles and as well as the as the area to be sprayed based on the different sizes of the nozzle used during spraying. Thickness of the dielectric layer is controlled by the concentration of the dielectric material in the solvent used during the spray process. The sprayed dielectric layers thickness on the pressed green magnets varies from about 1 μm to 1000 μm and preferably from about 1 μm to 500 μm and particularly preferred from about 10 μm to 400 μm. Subsequently Sm(Co,Fe,Cu,Zr)z magnetic particles are sprayed onto the coated magnet in thick layers which are pressed to make a green compact magnetic layer. Second and third dielectric layers with comparable or different thicknesses can be added following the above procedure. The number of sulfide-based dielectric layers is determined by specific applications of the sequentially laminated, permanent magnet of the invention.
The green, compact, laminated magnets of the invention are formed by pressing the laminates under a pressure of from 500 kgf/cm2 to 3000 kgf/cm2 in a magnetic field of from 1 kOe to 40 kOe. The green, compact, sequentially laminated, permanent magnet is then consolidated by sintering at from 1000° C. to 1250° C. for from 1 to 4 hours in vacuum or in an inert gas atmosphere such as an Ar atmosphere. The sintered product may be further homogenized and heat-treated to develop optimum magnetic properties.
In the present invention, the laminated, high electrical resistivity, rare earth, permanent magnets consist of sequential layers having different chemical compositions, each of which has a different function; namely:
(a) rare earth, permanent magnet layers,
(b) sulfide-based, dielectric layers surrounded by
(c) transition and/or diffusion reaction layers.
Rare earth permanent magnet layers are preferably comprised of rare earth permanent magnets, including RE-Fe—B and RE-Co-based permanent magnets, wherein RE is at least one rare earth element including Y (yttrium). Other rare earth, permanent magnet compositions suitable for use in the present invention are discussed below.
In a preferred embodiment, the rare earth magnet layer is represented by RE-Fe(M)-B comprised of from 10 to 40 weight % of RE and from 0.5 to 5 weight % of B (boron) with the balance of Fe(M) comprising Nd, Pr, Dy and Tb, with Nd particularly preferred. Further, it is preferred to use Dy up to 50 weight %, preferably up to 30 weight % of the total amount of RE. In an effort to improve the coercive force, M represents other optional metallic elements, such as Nb, Al, Ga and Cu. The addition of Co improves the permanent magnet, corrosion resistance and thermal stability. Co may be added up to 25 weight % based on the total amount of the RE-Fe—B-based magnet, as a replacement for Fe. An additional amount exceeding 25 weight % of Co unfavorably reduces the residual magnetic flux density, as well as the intrinsic coercive force. Nb is effective for preventing the overgrowth of crystals during processing while enhancing thermal stability. Since an excess amount of Nb reduces the residual magnetic flux density, Nb is preferably limited to up to 5 weight % based on the total amount of the RE-Fe—B-based magnet.
As stated above, the rare earth magnet layer can also include RE2Cor-based magnets with from 10 to 35 weight % of RE, 30 weight % or less of Fe, from 1 to 10 weight % of Cu, from 0.1 to 5 weight % of Zr, an optional small amount of other metallic elements such as Ti and Hf, with the balance comprising Co. The RE-Co-based, rare earth, permanent magnet is preferred based on its cellular microstructure consisting of cells with 2:17 rhombohedral type crystallographic structure and cell boundaries with 1:5 hexagonal crystallographic structure. In this magnet, the rare earth element is preferably Sm, along with optional other rare earth elements such as Ce, Er, Tb, Dy, Pr and Gd. When the amount of RE is lower than 10 weight %, the coercive force is low, and the residual magnetic flux density is reduced when RE exceeds 39 weight %. Although a high residual induction, Br, can be achieved by the addition of Fe, a sufficient coercive force can not be obtained when the amount exceeds 30 weight %. It is preferable to add Fe at least 5 weight % in order to improve Br. Copper, Cu, contributes to improving the coercive force. The addition of less than 1 weight % Cu shows improvement, while the residual magnetic flux density and coercive force are each reduced when the addition of Cu exceeds about 10 weight %.
The rare earth, permanent magnet, laminate layer can also comprise RECo5-based magnet with from 25 to 45 weight % of RE, and the balance Co. RE is preferably Sm along with other rare earth elements.
Other metallic or non-metallic elements can be present in Nd—Fe—B and Sm—Co based sequentially laminated magnets of the present invention at preferably less than 10 weight %. It is understood that the RE-Fe—B-based magnets and RE-Co-based magnets used in the sequentially laminated magnets of the present invention may include inevitable impurities such as C, N, O, Al, Si, Mn, Cr and combinations thereof.
The sulfide-based dielectric layer consists of substances selected from the group consisting of sulfide-based dielectric/semiconductor materials; where the sulfide-base includes: Al2S3, Sb2S3, As2S3, BaS, BeS, Bi2S3, B2S3, CdS, CaS, CeS, Ce2S3, WS, Cr2S3, CoS, CoS2, Cu2S, CuS, Dy2S3, Er2S3, EuS, Gd2S3, Ga2S3, GeS, GeS2, HfS2, Ho2S3, In2S, InS, FeS, FeS2, La2S3, LaS2, La2O2S, PbS, Li2S, MgS, MnS, HgS, MoS2, Nd2S3, NiS, NdS, K2S, Pr2S3, Sm2S3, Sc2S3, SiS2, Ag2S, Na2S, SrS, Tb2S, Tl2S, ThS2, Tm2S3, SnS, SnS2, TiS2, WS2, US2, V2S3, Yb2S3, Y2S3, Y2S3, Y2O2S, ZnS and ZrS2 or combinations of any of these materials with sulfides, oxysulfides, sulfides and oxysulfides, mixtures of: sulfides, sulfides and fluorides, and mixtures of sulfides, fluorides, oxy sulfides and/or oxyfluorides, oxysulfides, fluorides, oxyfluorides, mixtures of sulfides and fluorides.
The high electrical resistivity, sulfide-base, dielectric layers include mixtures with rare earth elements RE; wherein RE is selected from the group consisting of rare earth elements and mixtures thereof, and rare earth rich alloys. These rare earth rich alloys are different for different types of laminate layers. The following are some examples of the rare earth rich alloys suitable for inclusion in the sulfide-based, dielectric layer:
The transition and/or diffusion reaction layers are added or produced during the manufacturing process for the magnets of the invention to compensate for the reactions that takes place between the sulfide-based, dielectric layers and the rare earth, permanent magnet layers. These transition and/or diffusion reaction layers vary in composition depending on the types of magnet layers and dielectric layers present. The following are examples of rare earth, rich alloys suitable for transition and/or diffusion reaction layers:
The unexpected enhanced electrical resistivity and improved mechanical strength properties combined with excellent magnetic properties of the sequentially laminated, rare earth, permanent magnets of the present invention are further described in Examples 1 through 17, Tables 1 and 2, and
An anisotropic Sm(Co,Fe,Cu,Zr)z/Sm2S3 sequentially laminated magnet with increased electrical resistivity was synthesized by regular powder metallurgic processes consisting of sintering at from 1200° C. to 1220° C., solution treatment at from 1160° C. to 1180° C. and aging at from 830° C. to 890° C. This step was followed by a slow cooling to 400° C. The sequentially laminated, anisotropic magnet consisting of three sequential Sm(Co,Fe,Cu,Zr)z layers and three sequential Sm2S3 layers, shown in
The photograph set out in
Residual induction: Br=10.516 kG
Intrinsic coercivity: Hci>24.5 kOe
Maximum energy product: (BH)max=25.5 MGOe
The electrical resistivity of this sequentially laminated, rare earth, permanent magnet of the invention was unexpectedly increased by approximately 32 times (about 3000%) compared to a standard permanent magnet. Improved mechanical strength was also observed.
Residual induction: Br=10.73 kG
Intrinsic coercivity: Hci>24.5 kOe
Maximum energy product: (BH)max=25.5 MGOe
The electrical resistivity of this sequentially laminated, permanent magnet of the invention was unexpectedly increased by approximately 35 times (about 3000%) compared to a standard permanent magnet. Improved mechanical strength was also observed.
An anisotropic Sm(Co,Fe,Cu,Zr)z/Sm2S3 sequentially laminated, permanent magnet of the invention with increased electrical resistivity was produced according to a method of manufacturing of the invention; using regular powder metallurgical processes consisting of: sintering at 1195° C., solution treatment at 1180° C. and aging at 850° C. followed by a slow cooling to 400° C.
This anisotropic, sequentially laminated, permanent magnet consisting of sequential Sm(Co,Fe,Cu,Zr)z and Sm2S3 dielectric layers was produced by a one-step sintering process. As shown in optical micrograph (unetched)
Compared to a conventional magnet matrix, the electrical resistivity of the sequentially laminated magnet of the invention as shown in
An anisotropic Sm(Co,Fe,Cu,Zr)z/Sm2S3 sequentially laminated, permanent magnet with increased electrical resistivity was produced by the method of manufacture of the present invention using a powder metallurgical process consisting of: (a) sintering at 1195° C., (b) solution treatment at 1180° C., (c) aging at 850° C., followed by (d) a slow cooling 400° C.
Sequentially laminated, anisotropic magnets of the present invention consisting of sequential Sm(Co,Fe,Cu,Zr)z and Sm2S3 layers were produced by a one-step sintering process. As shown in the optical micrograph set out in
The electrical resistivity of the sequentially laminated magnet of the present invention was unexpectedly increased approximately 12 times over the magnet matrix, i.e., by about 1190%. Improved mechanical strength was also observed.
An anisotropic Sm(Co,Fe,Cu,Zr)z/Sm2S3 sequentially laminated, rare earth, permanent magnet of the invention with increased electrical resistivity and improved mechanical strength was developed by the method of the present invention comprising a powder metallurgical processes consisting of: (a) sintering at 1195° C., (b) solution treatment at 1180° C., (c) aging at 850° C., followed by (d) a slow cooling 400° C. Sequentially laminated, anisotropic magnets of the present invention consisting of sequential Sm(Co,Fe,Cu,Zr)z and Sm2S3 layers surrounded by diffusion reaction layers were by a one-step sintering process.
As shown in the optical micrograph set out in
The electrical resistivity of the magnet of the present invention shown in
An anisotropic Sm(Co,Fe,Cu,Zr)z/(Sm2S3+CaF2) sequentially laminated, rare earth, permanent magnet of the present invention with increased electrical resistivity and improved mechanical strength was produced by the method of the present invention comprising a powder metallurgical processes consisting of: (a) sintering at 1195° C., (b) solution treatment at 1180° C., (c) aging at 850° C., followed by (d) a slow cooling 400° C. A sequentially laminated, anisotropic magnet consisting of sequential Sm(Co,Fe,Cu,Zr)z magnetic layers and (Sm2S3+CaF2) dielectric layers were produced by a one-step sintering process.
As shown in
The electrical resistivity of this magnet shown in
An anisotropic Sm(Co,Fe,Cu,Zr)z/MnS sequentially laminated, rare earth, permanent magnet of the invention with increased electrical resistivity and improved mechanical strength was developed by the method of the present invention comprising a powder metallurgical processes consisting of: (a) sintering at 1195° C., (b) solution treatment at 1180° C., (c) aging at 850° C., followed by (d) a slow cooling to 400° C. Sequentially laminated, anisotropic magnets of the present invention consisting of sequential Sm(Co,Fe,Cu,Zr)z and MnS layers surrounded by diffusion reaction layers were by a one-step sintering process.
As shown in the optical micrograph in
The electrical resistivity of the magnet of the present invention shown in
Magnetic Properties and Electrical Resistivity Properties of sequentially laminated, permanent magnets of the present invention, as described in Examples 1 through 8 are summarized in Table 1 below
The present invention is further described by illustrative Examples 9 through 14 set out in Table 2, which provides additional examples of typical morphologies of the sequentially laminated, rare earth, permanent magnets of the invention having sequential: permanent magnet layers and dielectric layers surrounded by transition and/or diffusion reaction layers. The projected increase of the electrical resistivity of such sequentially laminated magnets of the invention which is substantially greater than the electrical resistivity of conventional magnets is achieved without loss in mechanical strength or in magnetic properties. Manufacturing methods of the present invention for the sequentially laminated, rare earth magnets include: sintering, hot pressing, die upsetting, spark plasma sintering, microwave sintering, infrared sintering and combustion driven compaction. In Table 2, x=1 to 6, unless otherwise specified.
The following conditions apply to each of Illustrative Examples in Table 2 as indicated therein by the appropriate symbol (#, +, and *) wherein:
