Tunable anisotropy of co-based nanocomposites for magnetic field sensing and inductor applications
11609281 · 2023-03-21
Assignee
Inventors
- Alex M. Leary (Pittsburgh, PA, US)
- Paul R. Ohodnicki (Pittsburgh, PA, US)
- Michael E. McHenry (Pittsburgh, PA, US)
- Vladimir Keylin (Pittsburgh, PA, US)
- Joseph Huth (Pittsburgh, PA, US)
- Samuel J. Kernion (Pittsburgh, PA, US)
Cpc classification
H01F1/15333
ELECTRICITY
G01R33/0052
PHYSICS
International classification
Abstract
A method includes producing an amorphous precursor to a nanocomposite, the amorphous precursor comprising a material that is substantially without crystals not exceeding 20% volume fraction; performing devitrification of the amorphous precursor, wherein the devitrification comprises a process of crystallization; forming, based on the devitrification, the nanocomposite with nano-crystals that contains an induced magnetic anisotropy; tuning, based on one or more of composition, temperature, configuration, and magnitude of stress applied during annealing and modification, the magnetic anisotropy of the nanocomposite; and adjusting, based on the tuned magnetic anisotropy, a magnetic permeability of the nanocomposite.
Claims
1. A method of controlling a nano-crystallization process in one or more geometries, the process comprising: producing an amorphous precursor to a nanocomposite, the amorphous precursor comprising a material that is substantially without crystals such that the crystals are not exceeding a 20% volume fraction of the material; performing devitrification of the amorphous precursor, wherein the devitrification comprises a process of crystallization; forming, based on the devitrification, the nanocomposite with nano-crystals that comprise an induced magnetic anisotropy; tuning, based on one or more of composition, temperature, configuration, and magnitude of stress applied during annealing and modification of a geometry of the nanocomposite, the magnetic anisotropy of the nanocomposite, wherein tuning comprises: varying the magnitude of the stress applied during annealing to apply a given stress value to a portion of the nanocomposite, wherein the given stress value is below 400 megapascals (MPa); and adjusting, based on the tuned magnetic anisotropy, a magnetic permeability of the nanocomposite at the portion of the nanocomposite to be below 100 based on the given stress value that is below 400 MPa.
2. The method of claim 1, wherein the nanocomposite has a ribbon geometry with a thickness of 10-35 microns.
3. The method of claim 1, wherein the nanocomposite has a wire geometry with a thickness of 1-20 microns and a glass coating thickness between 0.5-20 microns.
4. The method of claim 1, wherein tuning, based on the magnitude of stress applied during annealing comprises: applying stress to the amorphous precursor at an annealing temperature to create the nanocomposite, wherein the stress is applied in one or more of direct tension, compression, bending, and centripedal direction.
5. The method of claim 1, wherein tuning based on the magnitude of stress applied during annealing comprises: applying stress to the amorphous precursor by: applying heat with one or more thermal blocks in contact with to the amorphous precursor to evenly distribute heat; and using a feedback system to adjust annealing temperature and/or tension applied by a strain annealing system.
6. The method of claim 1, wherein modification of the geometry comprises modification of a size of at least one of the nano-crystals.
7. The method of claim 1, wherein the nanocomposite is a magnetic material that is included as a sensing element in a magnetic field sensor.
8. The method of claim 1, further comprising: adjusting a composition of the nanocomposite; and adjusting annealing parameters for use in the stress annealing; wherein tuning the magnetic anisotropy comprises: tuning, based on the adjusted composition and the adjusted annealing parameters, the magnetic anisotropy.
9. The method of claim 1, wherein the nanocomposite includes 30 atomic % or less of Iron (Fe), 30 atomic % or less of and Nickel (Ni), and 50 atomic % or less of one or more metals selected from the group comprising boron (B), carbon (C), phosphorous (P), silicon (Si), chromium (Cr), tantalum (Ta), niobium (Nb), vanadium (V), copper (Cu), aluminum (Al), molybdenum (Mo), manganese (Mn), tungsten (W), cobalt (Co) and zirconium (Zr).
10. The method of claim 1, wherein the nano-crystals comprise crystalline grains less than approximately 10 nanometers in average diameter embedded within an amorphous matrix.
11. The method of claim 1, wherein a Curie temperature of the nanocomposite is at least 600° C., and wherein the nanocomposite is configured for operating in temperatures up to at least 400° C.
12. The method of claim 1, wherein the induced magnetic anisotropy is tunable up to 29 kilojoules per cubic meter.
13. The method of claim 1, wherein the given stress value is below 350 megapascals (MPa).
14. The method of claim 1, wherein the permeability value is less than 90.
15. The method of claim 1, wherein the permeability value less than 80.
16. The method of claim 1, wherein the permeability value less than 70.
17. The method of claim 1, wherein the permeability value less than 60.
Description
BRIEF DESCRIPTION OF FIGURES
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DETAILED DESCRIPTION
(15) A nanocomposite soft magnetic alloy with tunable magnetic anisotropy, good thermal stability, and improved mechanical properties is described herein. Relevant alloys are Co-rich and include 30 atomic % or less of Iron (Fe) or Nickel (Ni) and 50 atomic % or less of one or more metals selected from the group comprising boron (B), carbon (C), phosphorous (P), silicon (Si), chromium (Cr), tantalum (Ta), niobium (Nb), vanadium (V), copper (Cu), aluminum (Al), molybdenum (Mo), manganese (Mn), tungsten (W), and zirconium (Zr). Amorphous precursors are created by a rapid quench technique and the nanocomposite is formed by thermal annealing under an applied strain field with or without an applied magnetic field. Tunable aniosotropies may be created greater than 30 kJ/m.sup.3 and the direction of the induced anisotropy is controllable by adjustments to composition and annealing technique. Relevant applications of the material include inductors, sensors, and motors.
(16) The techniques described herein enable the production and processing of soft magnetic nanocomposite materials with tunable anisotropies suitable for power electronic cores and for sensing elements in magnetic field sensors. The anisotropy induced by strain or field annealing is larger than anisotropies measured in other existing alloys and in strain annealing, requires less strain per unit of anisotropy. The induced anisotropy is tunable up to high energy densities that result in high or low permeabilities and is stable to high temperature. In addition to the requirement of lower stress per unit of induced anisotropy, the mechanical properties of the material are also improved compared to existing alloys that tend to become brittle after crystallization. These features overcome limitations in strain annealed Fe-based nanocomposite materials that become brittle during crystallization and limit the useful range of induced anisotropy.
(17) In an example, Co-rich FeCo nanocomposite materials comprising a crystalline phase are embedded within an amorphous matrix that show a strong response to stress annealing with improved mechanical properties. These materials consist of compositions (TL-TE-M) involving combinations of late transition metals (TL), early transition metals (TE), and metalloids (M). The metalloids and early transition elements improve the material's glass forming ability and limit diffusion and grain size. By adjusting the composition and the annealing parameters, the size and structure of the nanocrystals may be refined resulting in optimal magnetic properties.
(18) In both polycrystalline Fe.sub.1-xCox and amorphous (Fe.sub.1-xCox).sub.80B.sub.20 system, the sign of magnetostriction changes from positive to negative around 9:1 approaching the Co-rich compositions. (See O'Handley RC. Modern Magnetic Materials: Principles and Applications: Wiley Inter-Science, 1999.) Low loss materials require low magnetostriction so materials with small net positive or negative magnetostrictions are desired for strain annealing. Magnetostriction zero crossings exist in the Co-rich compositions of several ternary systems such as CoFeNi and CoFeMn. The net magnetostriction is the combination of the magnetostrictions of the amorphous and crystalline phases. Often the compositions of these phases differ from the master alloy composition due to partitioning during crystallization. The response of Co-rich nanocomposites to both field and stress annealing is very strong. In an example, a peak response to field annealing resulting in induced anisotropy (K.sub.u) is above 2 kJ/m.sup.3 near x=0.97 in (Fe.sub.1-xCox).sub.89Zr.sub.7B.sub.4. In another example, K.sub.u values approach 20 kJ/m.sup.3 in similar compositions using strain annealing. The strain annealing response of Co-rich nanocomposites is twice the strain annealing response measured in Fe-rich nanocomposite compositions as measured on a per-unit applied stress basis. Not only does a given stress level produce higher induced anisotropy in Co-rich materials, but higher induced anisotropies are also achievable. The Curie temperature of the amorphous phase in Co-rich alloys can exceed 600° C. compared to approximately 400° C. or less in Fe-rich compositions. Additionally, whereas most nanocomposite alloys to date are brittle following the annealing process, these alloys have improved mechanical properties and in particular strain to fracture.
(19) In order to overcome the low thermal stability of amorphous materials, the nanocomposite form is preferred. These materials are formed by a devitrification of the amorphous precursor with suitable compositions to limit grain growth. The amorphous precursor is produced by a rapid solidification technique such as melt spinning or wire drawing. Co-rich nanocomposite alloys can undergo multiphase crystallization resulting in a mixture of body centered cubic (bcc), face centered cubic (fcc), and hexagonal close packed (hcp) grains. Enrichment in either Co, Fe, and/or the TE and M components of the composition cause fluctuations in local compositions compared to the nominal ingot composition. The zero crossing for magnetostriction in FeCo alloys occurs near 91% Co and serves as a guideline for composition and processing decisions depending on the desired application. Suitable choice of composition and annealing procedures result in anisotropy energy densities above 20 kJ/m.sup.3 corresponding to relative permeabilities below ˜20.
(20) Referring to
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(22) Referring to
(23) It is advantageous for the crystallization process to occur quickly in strain annealing to allow for high production rates. Referring to
(24) Referring to
(25) Referring to
(26) Referring to
(27) Referring to
(28) The magnetic material is formed by rapid solidification from pre-alloyed ingots with compositions based on Co, containing 30 atomic % or less Fe and/or Ni, and 50 atomic % or less of one or more metals selected from the group comprising boron (B), carbon (C), phosphorous (P), silicon (Si), chromium (Cr), tantalum (Ta), niobium (Nb), vanadium (V), copper (Cu), aluminum (Al), molybdenum (Mo), manganese (Mn), tungsten (W), and zirconium (Zr).
(29) The amorphous precursor undergoes strain annealing, a processing technique in which a stress field is applied to the ribbon at a desired temperature for a desired duration of time. The product of strain annealing is a nanocomposite consisting of crystallite particles of nanometer size scale embedded in the residual amorphous matrix. The strain annealed nanocomposite ribbon exhibits magnetic anisotropy.
(30) The induced anisotropy is tuned by varying the applied stress during the annealing process and the anisotropy response is linear with stress to a threshold value that varies for each alloy. In some alloys, stresses may be applied up to 1 GPa without material failure resulting in low permeabilities for Co-rich compositions with negative magnetostrictions.
(31) Low permeability level (100 to 15) combined with flat B-H loop and low watt loss allows application of the claimed material in various inductors and energy storage devices instead of powder cores or gapped cores. In contrast with powder cores, the tape wound cores made of the Co-rich alloys can be wound practically of any size, whereas powder core size usually is not more than about 6-8 in., and limited by required compaction pressure and strength of die tool steel. Gapped cores have significant fringing flux that causes additional watt loss, heating of adjacent metallic parts, and EMI/RFI problems, in contrast with gapless tape wound cores made of strain annealed claimed Co-rich alloys.
(32) Surface roughness in the sensing element leads to anomalous losses that degrade sensor performance. Coating of a conductive material to reduce surface roughness of the ribbon reduces stray fields caused by surface roughness and improves sensor performance.
(33) The field sensitivity peak for GMI sensors occurs when the external field approaches the level of the induced anisotropy field. Larger anisotropy fields in the strain annealed Co-based alloys described above allow for wider and tunable ranges of sensor operation in GMI sensors that employ these materials as sensing elements in ribbon or wire form. Similarly, tunable permeability in inductor cores is advantageous to tailor a magnetic material to a particular application. Low permeability cores exhibit significant advantages for applications requiring high power transformation and large stored energies. The larger anisotropy fields in the strain annealed alloys described above allow for lower and tunable permeabilities for such applications.
(34) Referring to
(35) Referring to
(36) In an example, a material includes cobalt (Co), 30 atomic % or less of Iron (Fe) or Nickel (Ni) and 50 atomic % or less of one or more metals selected from the group comprising boron (B), carbon (C), phosphorous (P), silicon (Si), chromium (Cr), tantalum (Ta), niobium (Nb), vanadium (V), copper (Cu), aluminum (Al), molybdenum (Mo), manganese (Mn), tungsten (W), and zirconium (Zr). In this example, the material has a composite structure with crystalline grains less than approximately 50 nanometers in average diameter embedded within an amorphous matrix. Compared to the nominal composition, the amorphous matrix that surrounds the grains becomes enriched in early transition metals and limits further grain growth during crystallization. The material is formed through a thermo-mechanical process that results in an amorphous precursor material and includes at least one mechanical operation and at least one thermal operation. The mechanical operation is also performed under elevated temperature conditions.
(37) In this example, at least one thermal operation comprises a rapid solidification operation that includes formation of amorphous wires and/or ribbons by melt-spinning with and without glass coating, in-rotating water spinning, sputtering, and electrodeposition (see Phan, et al. Prog. Mat. Sci. 53 (2008). Raw materials used to create the desired composition should be of sufficient quality to limit impurities and can be in powder, ingot, or crushed ingot forms. Melt spinning is a technique used for rapid cooling of liquids. A wheel is cooled internally, usually by water or liquid nitrogen, and rotated. A thin stream of liquid is applied to the wheel either by jet casting a free stream or through a confined puddle formed between the nozzle and wheel surface and cooled, causing rapid solidification. This technique is used to develop materials that require extremely high cooling rates in order to form, such as metallic glasses. The cooling rates achievable by melt-spinning are on the order of 10.sup.4-10.sup.7 kelvins per second (K/s).
(38) In another example, at least one mechanical operation comprises application of a tensile strain along a longitudinal axis of a ribbon or a wire, during an elevated temperature annealing treatment above approximately 200° Celsius to control a permeability of the material. In this example, the applied tensile strain is less than approximately 350 megapascal (MPa) and an effective induced anisotropy is tunable up to 29 kJ/m.sup.3. In this example, a resulting anisotropy energy density per megapascal (MPa) of the applied tensile strain is greater than
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This sensitivity to strain annealing attractive compared to
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in FeSiNbBCu nanocomposites. Additionally, FeSiNbBCu ribbons become brittle following crystallization and tend to fracture at low stresses (above 100 MPa), complicating strain annealing of these materials.
(41) In another example, the material is included in a magnetic sensing material, an inductor, or a motor design. The fine grain structure in the nanocomposite averages the magnetocrystalline anisotropy between adjacent grains and leads to low coercivity. Low coercivity allows for low loss switching in inductive applications.
(42) In another example, the material is annealed in a magnetic field with applied stress. Here, the material is supported in a magnetic field that is oriented in a desired direction while the sample is heated to through the chosen annealing profile. The ribbon can be wound into a core or unwound depending on the desired application.
(43) In still another example, the material (from which the nanocomposite is made) is formed from an alloy that is dilute or substantially free of hafnium (Hf), zirconium (Zr), and titanium (Ti). These elements oxidize easily and greatly complicate planar flow casting where the casting atmosphere contains moderate amounts of oxygen. Typically, planar flow casting of compositions with Hf, Zr, and/or Ti require the entire casting process to be contained within a vacuum chamber which significantly increases production cost and complexity. In still another example, the alloy is an as-cast alloy, and an amorphous precursor of the as-cast alloy has a Curie temperature greater than approximately 600° Celsius. The Curie temperature of the amorphous matrix is typically lower than the Curie temperature of the crystalline grains. Operating temperatures approaching the amorphous phase Curie temperature result in increased coercivity and higher losses as the random anisotropy between grains breaks down. Generally, an as-cast material is material in ribbon or wire form that is mostly or wholly amorphous that is the precursor material to the annealing treatment necessary to form the nanocomposite.
(44) In still another example, the nanocomposite with the tunable anisotropy is used as a magnetic field sensor in a sensing element, an inductor core, or a transformer. The tunable anisotropy affects the magnetic permeability of the nanocomposite, making the nanocomposite well suited for use as a magnetic field sensor. Permeability controls the skin depth, the saturation point of the material, and the dynamic magnetization mechanism and the ideal level depends on the application. Sensors that rely on Giant Magnetoimpedance (GMI) are sensitive to changes in skin depth over a limited frequency range and the ability to induce well defined anisotropy leads to high sensitivity at fields near the induced anisotropy field. The fluxgate magnetometer design uses a soft magnetic core that is alternately driven to saturation by a drive coil and is sensitive to the saturation point. When placed in an external field, the core saturates asymmetrically producing even harmonics proportional to the field strength according to Faraday's law. All sensor performance is dictated by the signal to noise level and Barkhausen noise arising from random domain wall movements is a significant noise source in magnetic sensors. Induced anisotropies control the magnetization mechanism by reducing domain wall motion and increasing magnetization changes by rotation. Because the ideal permeability for a magnetic field sensor depends upon the specific application and the type of device employed, the ability to tune induced anisotropies over a large range with resultant linear hysteresis loops allows for a broad range of applications and enhanced device compatibility.
(45) In an example, the nanocomposite materials described here have increased ductility, relative to other soft magnetic nanocomposite materials. Generally, ductility is a solid material's ability to deform under tensile stress and ductility in ribbon form is generally determined by a simple bend test. Although the mechanistic origin of an enhanced mechanical ductility for high Co-containing nanocomposite alloys as compared to Fe-rich alloys has not yet been elucidated, it has been demonstrated empirically for a number of different alloy systems. In this example, the nanocomposite material is capable of being stamped for use in one or more of a motor stator and a rotor. The lower losses in the nanocomposite material allows for higher switching frequencies and speeds than is capable in Si-steel rotors. Suitable designs also may lead to higher efficiency.
(46) In this example, the nanocomposite material in the motor stator or in the rotor is capable of operation at approximately 200° Celsius. This is above the useful range of amorphous materials and is attributed to the higher Curie temperature and stability of the nanocomposite structure.
(47) In an example, the material is capable of being planar flow cast without a protective vacuum. Planar flow casting within a protective vacuum chambers is required when the composition is highly sensitive to oxidation so the process is conducted in a carefully controlled atmosphere.
(48) In still another example, the nanocomposite material is a wire in a sensing element that is included in a wirelessly interrogable device, such as a wirelessly interrogable acoustic sensor.
(49) In still another example, the material in the wire form is capable of operation at temperatures above 150° Celsius. Amorphous materials tend to change structure and properties near this temperature and are not suited for long term, high temperature use at such elevated temperatures. Fe-rich nanocomposite alloys tend to have relatively low Curie temperatures of the amorphous phase which impart a strong temperature dependence of the response which is not desirable for a high temperature sensing device.
(50) Referring to
(51) In this example, the process also includes performing stress annealing (260) on the nanocomposite to modify the nano-crystals. There are various ways in which stress annealing is performed, e.g., pulling the material (in ribbon form) through a furnace, spreading the material out with heat and stress, applying lubricated thermal blocks to the ribbon, and other techniques for applying heat to the ribbon to promote crystallization in a particular geometry. In this example, the process includes tuning (262), based on an amount of stress annealing, a magnetic anisotropy of the nanocomposite. In this example, there is a linear relationship below a limiting threshold between the amount of stress annealing and the amount of induced magnetic anisotropy. That is, the tensile stress imparts the magnetic anisotropy, which in turn affects the magnetic permeability of the nanocomposite material. In this example, the process includes adjusting (264) the magnetic permeability of the nanocomposite material, e.g., to a level that is satisfactory for use of the nanocomposite material as a magnetic sensing element. Amorphous structures are metastable and the local stress and magnetic field present during crystallization determines the structure that results in the lowest energy following crystallization. Annealing without applied stress or a magnetic field results in a mainly isotropic structure. Annealing with a global stress and/or magnetic field results in pair ordering, preferred orientations of atoms/defects, and/or residual stress that remains at operating temperatures. All mechanisms can lead to magnetic anisotropy by non-uniform magnetocrystalline anisotropy and/or coupling to stress through non-zero magnetostriction. In another example, after formation of the amorphous precursor (by melt spinning, a powder method, or wire drawing), the material is devitrified under stress (e.g., via stress crystallization) with or without an applied field.
(52) Other embodiments are within the scope and spirit of the description claims. Additionally, due to the nature of software, functions described above can be implemented using software, hardware, firmware, hardwiring, or combinations of any of these. Features implementing functions may also be physically located at various positions, including being distributed such that portions of functions are implemented at different physical locations. The use of the term “a” herein and throughout the application is not used in a limiting manner and therefore is not meant to exclude a multiple meaning or a “one or more” meaning for the term “a.” Additionally, to the extent priority is claimed to a provisional patent application, it should be understood that the provisional patent application is not limiting but includes examples of how the techniques described herein may be implemented.
(53) It will thus be seen that the objects set forth above, among those made apparent from the preceding description, are efficiently attained and, because certain changes may be made in carrying out the above method and in the construction(s) set forth without departing from the spirit and scope of the disclosure, it is intended that all matter contained in the above description and shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.
(54) A number of exemplary implementations of the invention have been described. Nevertheless, it will be understood by one of ordinary skill in the art that various modifications may be made without departing from the spirit and scope of the invention.