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    • 专利摘要:
    Permanent magnet, obtaining procedure and uses. The present invention relates to a permanent magnet comprising hard magnetic particles and a soft magnetic structure with an aspect ratio greater than or equal to 3 and with a monodomain magnetic structure. Furthermore, the present invention relates to the method of obtaining said magnet and the use of said magnet as part of a generator or a motor vehicle. The present invention falls within the field of magnetic materials and their industrial applications. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2768433A1
    申请号:ES201831258
    申请日:2018-12-20
    公开日:2020-06-22
    发明作者:Minguez Jesús Carlos Guzmán；Arche Luis Moreno；Michelena Adrián Quesada；Lozano José Francisco Fernández；García Federico Mompean；Hernández Mar García；Lucas Pérez；Gomez Sandra Ruiz；Dmitry Berkov；Sergey Erohkin
    申请人:General Numerics Res Lab E V；Consejo Superior de Investigaciones Cientificas CSIC；Universidad Complutense de Madrid；
    IPC主号:
    专利说明:

    [0002] Permanent magnet, obtaining procedure and uses
    [0004] The present invention relates to a permanent magnet comprising hard magnetic particles and a soft magnetic structure with an aspect ratio greater than or equal to 3 and with a monodomain magnetic structure. Furthermore, the present invention relates to the method of obtaining said magnet and the use of said magnet as part of a generator or a motor vehicle.
    [0006] The present invention falls within the field of magnetic materials and their industrial applications.
    [0008] BACKGROUND OF THE INVENTION
    [0010] Permanent magnets are crucial materials since they allow us to store, supply and convert electrical energy into mechanical energy and vice versa, in such a way that better magnets lead to greater energy efficiency.
    [0012] The most competitive magnets are based on rare earths, however the crisis associated with these elements has highlighted the economic, geostrategic and environmental importance of finding alternative magnets of competitive performance that reduce our dependence on rare earths.
    [0014] One way to reduce the rare earth content in permanent magnets without worsening or maintaining their magnetic properties is to combine a rare earth based hard magnetic material and a ferritic hard magnetic material of an oxidic nature as claimed by CN106312077.
    [0016] CN105006325 discloses a method for preparing composite ferrite powder with an exchange coupling effect and single-phase magnetic behavior through grinding between a soft magnetic phase of FeB and a hard magnetic phase of ferrite according to a mass ratio of 1: 1 . With the adopted method, the exchange coupling effect can be realized without the need for high sintering temperature. However, the resulting product does not exhibit permanent magnet behavior since it exhibits soft magnetic behavior with remaining magnetization values of less than 0.12 T.
    [0018] CN101481241 refers to a method of preparing a nanocrystalline permanent magnet, characterized in that a nanocrystalline powder of barium ferrite with hard magnetic behavior and a nanocrystalline powder of nickel-copper-ferrite with soft magnetic behavior are mixed, dried and thermally treated obtaining a complex nanocrystalline phase that has a saturation magnetization greater than 0.3 T, and a coercive field between 0.5 and 0.8 T; similar in terms of saturation magnetization to those obtained for the nanocrystalline powder of barium ferrite.
    [0020] WO2017137640A1 claims hybrid permanent magnet micro-composites comprising an oxide-based ferrite hard magnetic material, a metal-based soft magnetic material and an organic coupling agent. The microcomposite shows improvements of 25% in the remanence magnetization with respect to the ferrite phase, of isotropic powders without magnetic orientation. In the obtaining procedure, the presence of a coupling agent is required to protect the soft magnetic material that has particles with sizes greater than 200 nm from oxidation. The WO2017137640A1 material is an isotropic powder that exhibits an improvement in remanence over an isotropic ferrite powder; however the invention of WO2017137640A1 does not cover the case of anisotropic materials (i.e. magnetically oriented). Thus, although the isotropic composite has a greater remanence, it does not necessarily imply that this improvement can be transferred to a magnetically oriented or anisotropic composite.
    [0022] Therefore, it is necessary to develop permanent magnets that do not contain rare earths and that have improved magnetic properties with respect to the state of the art.
    [0024] DESCRIPTION OF THE INVENTION
    [0026] In a first aspect, the present invention relates to a permanent magnet (hereafter "the magnet of the invention"), characterized in that it comprises
    [0027] • Hard magnetic particles with diameters between 100 nm and 100 pm and of ferrite or hexaferrite composition of the formula MeFe ^ O 19 , where Me is a divalent alkaline earth metal selected from Sr + 2, Ba + 2 and any of their combinations;
    [0028] • A soft magnetic structure with an aspect ratio greater than or equal to 3 and with a monodomain magnetic structure,
    [0030] or of a composition selected from Fe, Co, a Fe alloy, a Co alloy, a FeCo alloy, a FeNi alloy, a FeSiB alloy, or a combination of the foregoing,
    [0031] or that it is passivated with an amorphous surface oxide layer with a thickness less than or equal to 10 nm,
    [0033] or and where the weight percentage of the soft magnetic structure is between 1% and 40% with respect to the final weight of the magnet, and
    [0034] where the hard magnetic particles and the soft magnetic structure are magnetically oriented in the same direction.
    [0036] The term "hard magnetic nanostructure" is understood in the present invention as that particle with a size between 100 nm and 100 pm that has a coercive field greater than 240 kA.m-1 and a saturation magnetization less than 525 kA.m -one.
    [0038] By the term "soft magnetic nanostructure" is understood in the present invention as that structure with an aspect ratio greater than or equal to 5 that has a saturation magnetization greater than 700 kA.m-1.
    [0040] The following equivalences between magnetic units are used herein: 1T ~ 796 kA.m-1; 1T = 10,000 G = 10,000 Oe = 795,775 kA.m-1
    [0042] By the term "aspect ratio" is meant the relationship that occurs between the largest dimension of the particle, that is, the length, and the smallest dimension that in the case of a particle with a cylindrical section would correspond to the diameter.
    [0044] By the term "magnetic anisotropy" is meant the non-homogeneity of the magnetic properties when measured in different directions of space. A material will be magnetically harder the higher its total magnetic anisotropy.
    [0045] By the term "magnetrocrystalline anisotropy" is meant the non-homogeneity of the magnetic properties along specific axes of the crystal structure.
    [0047] By the term "shape anisotropy" is meant the magnetic response as a consequence of the geometric shape of the material or the particles that constitute it. Thus, in a material with an elongated shape (for example, a needle), the magnetization will try to arranged parallel to its main axis, whereas in a two-dimensional material (a disk or a tape), the magnetization will prefer to be arranged in the plane.
    [0049] In a particular embodiment of the magnet of the present invention, the soft magnetic structure is characterized by having an aspect ratio greater than or equal to 3, more particularly greater than or equal to 5.
    [0051] An aspect ratio greater than or equal to 5 of the soft magnetic structure results in high remanence magnetization and a monodomain structure as a consequence of its shape anisotropy. The aspect ratio of the soft magnetic structure is of special relevance to the formation of the permanent magnet of the present invention. The physical mechanism that is at the origin of this response, and without being limiting it, is as follows: the system seeks to minimize the accumulation of magnetic poles and their magnetization is aligned with the longitudinal axis of the particle. The alignment of the magnet with the longitudinal axis of the soft magnetic structure of the present invention is maximized above a certain aspect ratio. Electromagnetic simulation calculations establish that for a diameter / caliber of 30 nm and an aspect ratio greater than 3, 83% of spins aligned in the longitudinal direction of the anisotropic soft magnetic structure are reached. When the nanowire has an aspect ratio greater than or equal to 5, it reaches its optimal monodomain state, that is, all its magnetization is oriented in the same direction.
    [0053] In another particular embodiment of the magnet of the present invention, the soft magnetic structure is a wire with a length of between 150 nm and 60 pm and a gauge of less than or equal to 100 nm, preferably less than 50 nm.
    [0055] In a preferred embodiment of the magnet of the present invention, the magnetic structure Soft is passivated with an amorphous surface oxide layer with monodomain structure and thickness less than 10 nm.
    [0057] The surface oxide coating or layer of the soft magnetic structure is an oxide with a thickness of less than or equal to 10 nm, preferably less than or equal to 7 nm, and especially preferably less than or equal to 5 nm. The oxide layer is generated during the manufacturing process by exposing the soft metallic magnetic structure of magnetically soft material to an air atmosphere in a controlled manner during the drying process of the solvents used in the removal of washing chemicals of said materials. Said oxide layer acts as a coating that protects the metallic material from complete oxidation. The oxide layer of the coating is characterized by the absence of long-range crystalline order, thus constituting an amorphous oxide layer. Likewise, the oxide layer of the coating, in addition to protecting it from subsequent oxidation, produces a surprising effect that is related to the reduction of the effective diameter of the soft magnetic structure that contributes to stabilizing the mono-domain state of the soft magnetic structure.
    [0059] When the soft magnetic structure is a wire with a length of between 150 nm and 60 pm and a gauge less than or equal to 100 nm, that is, as a nanowire, said nanowires are kept in a single-domain state and increase the remanence magnetization value. of hard magnetic particles. Nanowires are characterized by presenting an oxide layer as a coating that appears during the partial oxidation of the surface when exposed to air after the membrane dissolution processes where they have grown. The oxide layer of the nanowire coating protects them from complete oxidation and increases the effective aspect ratio of the magnet by reducing the magnetic diameter of the metal phase inside.
    [0061] A second aspect of the present invention refers to the process for obtaining the magnet of the invention characterized in that it comprises the following steps:
    [0062] a) electrodeposition of the soft magnetic structure in the presence of a porous membrane, where the pores of the membrane correspond to the dimensions of the soft magnetic structure,
    [0064] b) removal of the membrane by dissolution,
    [0065] c) drying the magnetic structure obtained in step (b) at a temperature between 30 ° C and 120 ° C and in the presence of an air atmosphere,
    [0066] d) Ultrasound mixing of the soft magnetic structure obtained in step (c) with the hard magnetic particles in a liquid ethanol medium until obtaining a homogeneous mixture, and
    [0068] e) drying and compacting the product obtained in step (d) in the presence of a magnet of between 0.2 T and 1.25 T and under a pressure of between 150 Kg / cm2 and 1500 Kg / cm2.
    [0070] Step a) of the procedure uses a porous support as a standard element for the growth of the soft magnetic phase nanowires. In a preferred embodiment of the process of the present invention, the porous support consists of a membrane that has transverse pores where each of the pores has a diameter of between 10 nm and 300 nm, a pore length greater than or equal to 100 pm and a pore density of between 105 to 109 pores per cm2.
    [0072] In another preferred embodiment of the present invention, the material that is used for the porous membrane is polymer-based, for example polycarbonate, polyester, polystyrene, polystyrene-glyceryl polymethacrylate or polyvinylidene fluoride; or an oxide, such as a porous aluminum oxide membrane.
    [0074] In a more particular embodiment of the invention, the porous membrane used for the growth of the nanowire-shaped soft magnetic structure is an etched nanoporous polycarbonate membrane.
    [0076] The selected membrane is electroded on one of its faces with a metallic layer, preferably Au, using the thermal evaporation deposition technique. In the present invention an Au electrode with a thickness of 100nm is preferably deposited.
    [0078] In step a), the electrodeposition of the soft magnetic structure is carried out using an aqueous solution of boric acid, where the sulfate salts corresponding to the metal cations of the corresponding compositions are diluted. The concentration of metal cation salts in the aqueous boric acid solution is between 0.04M and 0.3M. Preferably, the solution Boric acid solution contains a concentration of 0.09 M C 0 SO 4 and 0.1 M FeSO 4 and is at a pH of 2.7.
    [0080] In step a) the growth of the soft magnetic structure is carried out by electrochemical deposition by applying a voltage for a time determined by the pore density of the porous membrane and the diameter thereof. In a particular embodiment of the present invention, a voltage of -1.1 V applied between 100 s and 3000 s has been used. using a porous membrane 25 mm in diameter and 6 ^ m thick that has transverse pores, with a pore density of 6108 pores / cm2, with a nominal pore diameter of 30 nm and a real pore of 50 nm.
    [0082] In step b) of the process of the present invention the porous membrane is removed by dissolution. It is a chemical attack to remove the contact electrode and the membrane, keeping the magnetic structure soft.
    [0084] The chemical attack of the membrane contact electrode is carried out by iodide solutions, for example molecular iodine and potassium iodide. In a particular embodiment of the present invention, the chemical attack of the Au layer that acts as a contact electrode of the membrane is carried out by washing with an aqueous solution of 25 g / l of diiode and 100 g / l of KI.
    [0086] The chemical attack of the membrane is carried out by means of a washing routine in different solvents in order to obtain the soft magnetic structure free of residues from said membrane. Solvents for removing polymer-based membranes are common solvents for such polymers such as toluene, xylene, ethyl acetate, ethyl acetate, dichloromethane, chloroform, acetone, alcohol, perchlorethylene, methyl chloride, tetrahydrofuran, dimethylformamide, diethyl ether and acid. formic. The membrane dissolution strategy combines sequential washing in different solvents and the use of sonication processes by ultrasound and centrifugation at each stage to obtain the soft magnetic structure.
    [0087] In a particular embodiment of the method of the present invention, the chemical attack to remove the membrane and the contact electrode is carried out by means of the following cleaning routine that comprises the following steps:
    [0088] - Elimination of Au with an aqueous solution of 25g / l of I2 and 100g / L of KI, - 4 washes of 2 ml of dichloromethane,
    [0089] - 4 washes of 2 ml acetone,
    [0090] - 2 washes of 2 ml ethanol, and
    [0091] - 2 washes of water of 2 ml.
    [0093] In step (c) of the process, the drying of the soft magnetic structure obtained in step (b) is carried out by means of a heat treatment in an oven at a temperature between 30 ° C and 120 ° C and in the presence of an atmosphere of air. In this step (c) controlled oxidation (passivation) of the surface of the soft magnetic structure occurs. In a particular embodiment of the process of the present invention, drying of step (c) is carried out in an oven at 60 ° C for 1 hour in an air atmosphere. The product resulting from step c) is a powdery material corresponding to the passivated soft magnetic structure.
    [0095] In step (d) of the process of the present invention, the soft magnetic structure obtained in step (d) is homogeneously mixed, with the help of ultrasound, with the hard magnetic particles in a liquid medium.
    [0097] The mixing process of the compositions is carried out by usual means in semi-liquid medium or in liquid medium. By the term "semi-liquid" mixture is meant in the present invention a mixture such as that described in the permanent magnet that has a percentage of solvent in the composition such that the product does not behave as a paste or as a solid without presenting the characteristic behavior of a liquid or suspension. The liquid medium used corresponds to a solvent selected from water, alcohol, acetone, hydrocarbon or a mixture of various solvents.
    [0099] An example of mixing in "liquid medium" corresponds to a suspension of the mixture by 20% by weight in ethanol and mechanical stirring by means of a propeller stirrer rotating at 150 rpm for 10 minutes and with sonication by ultrasound.
    [0100] An example of mixing in "semi-liquid" medium is carried out in an intensive laboratory mixer type Eirich containing 10% by weight of water.
    [0102] Step (e) of the process of the present invention refers to the drying and compaction of the product obtained in step (d) in the presence of a magnet of between 0.20 T and 1.25 T and under a pressure of between 150 Kg / cm2 and 1500 Kg / cm2. The drying of step (e) is carried out by heat treatment in an oven at a temperature between 30 ° C and 120 ° C and in the presence of a selected atmosphere of air.
    [0104] On the other hand, the drying carried out in step (d) can be complete or partial.
    [0106] A product that maintains a weight percentage of water between 3% and 8% is called “partially dry product”. The advantage of the partially dry product is that it favors the subsequent shaping process by pressing in the presence of a magnetic field such as that generated by a magnet between 0.2 T and 1.25 T and under pressure between 150 Kg / cm2 and 1500 Kg / cm2. The process of forming under pressure in the presence of a magnetic field allows the magnetic orientation of the particles in the mixture, maximizing the magnetic anisotropy of the compact. The presence of a semi-liquid mixture (partially dry product) favors both the compaction and the orientation of the particles in the magnetic field by acting the liquid medium as a lubricant.
    [0108] A "completely dry product" is a product that contains an amount of solvent less than 0.5% by weight with respect to the product obtained in step (d).
    [0110] The compaction process of the partially or completely dry product is carried out by injection molding using thermoplastic material and working at the usual injection temperature for said thermoplastic. In a particular embodiment of the compaction process of step (e), the polymer used for the injection molding process is a polyamide type polymer.
    [0111] Magnetization of the product obtained in step (d) can be carried out by applying a stationary magnetic field with an electromagnet or with coils fed with an alternating current source.
    [0113] A third aspect of the invention relates to the use of the permanent magnet of the present invention as part of a generator. Examples of generators are an electric turbine generator, a flywheel, and a wave generator.
    [0115] Another aspect of the invention relates to the use of the permanent magnet of the present invention as part of a motor vehicle, specifically as part of a hybrid or electric motor, as part of the electric window lift system, as part of the power steering system.
    [0117] Throughout the description and claims, the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages, and features of the invention will emerge in part from the description and in part from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    [0119] BRIEF DESCRIPTION OF THE FIGURES
    [0121] FIG. 1. Transmission electron microscopy images of a FeCo nanowire of 100 nm in diameter / gauge and> 800 nm in length, covered by an oxide layer of thickness between 4-10 nm.
    [0123] FIG. 2. Thermogravimetric analysis (TGA) of 30 nm diameter / gauge FeCo nanowires carried out in air at a temperature between room temperature and 900 ° C.
    [0125] FIG. 3. Magnetization curve against an applied magnetic field of 30 nm FeCo soft magnetic nanowires with an aspect ratio n = 200.
    [0127] FIG. 4. Magnetization curves against the applied field of the hard magnetic particles of ferrite (1), of the soft magnetic nanowires (2), and of the I6 magnet that it comprises 60% of ferrite hard magnetic particles and 40% by weight of soft magnetic nanowires (3).
    [0129] FIG. 5. Magnetization curve against an applied field of an I8 magnet comprising 80% by weight of hard magnetic strontium ferrite particles and 20% by weight of spherical Fe nanoparticles with a diameter of 25 nm.
    [0131] FIG. 6. Scheme of a simulation of the spin structure inside a nanowire with an aspect ratio n = 3.
    [0133] FIG. 7a. Simulated data of the evolution of the coercive field with the length of a 30 nm diameter cylindrical nanowire.
    [0135] FIG. 7b. Simulated data of the evolution of the remanence to saturation ratio (Mr / Ms) with the length of a cylindrical nanowire of 30 nm in diameter.
    [0137] EXAMPLES
    [0139] The invention will now be illustrated by tests carried out by the inventors, which shows the effectiveness of the product of the invention.
    [0141] Example 1. Manufacture of FeCo soft magnetic nanowires
    [0143] FeCo nanowires, with diameters of 30, 50, and 100 nm, were grown by electrodeposition within the pores of a polycarbonate membrane on which an Au electrode had grown on one side. 3 different pore sizes were used: 30, 50 and 100 nm. All the membranes used were 6 pm high.
    [0145] In a second step, both the membrane and the Au electrode were dissolved to obtain the nanowires in powder form. The membrane dissolution method was performed following a cleaning routine that used dichloromethane, acetone, ethanol and aqueous iodide solutions as solvents. It was necessary to repeat the dissolution process several consecutive times, on the order of 5, in order to completely remove the membrane.
    [0146] A drying step was then carried out in an oven at a temperature of 60 ° C for 1 hour in an air atmosphere, generating an oxide layer of approximately 5 nm that covers the nanowires.
    [0148] The electrodeposition conditions used were:
    [0150] A 25 mm diameter membrane, with a pore density of 6108 pores / cm2, with a nominal pore size of 30 nm and a real pore of 50 nm.
    [0152] An Au electrode deposited by thermal evaporation with a thickness of 100 nm. An aqueous solution of 0.4 M H 3 BO 3 , 0.09 M CoSO 4 and 0.1 M FeSO 4 with a pH of 2.7.
    [0154] A voltage of -1.1V for 250s for 30nm, 500s for 50nm and 2800s for 100nm, respectively.
    [0156] The cleaning routine consists of:
    [0157] • Elimination of Au with an aqueous solution of 25 g / l of I 2 and 100 g / l of KI.
    [0158] • 4 washes of 2 ml of dichloromethane.
    [0159] • 4 washes of 2 ml acetone.
    [0160] • 2 washes of 2 ml ethanol.
    [0161] • 2 washes of water of 2 ml.
    [0163] Each wash is sonicated for one minute in a device labeled "ultrasons sonicator" with a power of 50 W during 60 Hz and centrifuged for 1 min at 7000 rpm.
    [0165] Figure 1 shows a transmission electron microscopy image of a FeCo nanowire of 30 nm in diameter / gauge and> 800 nm in length, showing the existence of the oxide coating of the nanowire with a thickness of between 4 nm and 10nm. The oxide layer corresponds to the lightest part near its edge and is characterized by not having a crystalline order, being amorphous. The metallic central part is dark and presents characteristic crystalline planes.
    [0166] This coating acts as a protective layer and prevents complete oxidation of the nanostructure.
    [0168] Figure 2 shows a thermogravimetric analysis (TGA) of 30 nm diameter / gauge FeCo nanowires carried out in air between room temperature and 900 ° C, in which the oxidation process thereof is observed. The TGA demonstrates that the nanowires are stable in an air atmosphere and that temperatures above 300 ° C are required to start the oxidation process.
    [0170] Furthermore, the oxide coating reduces the effective diameter of the nanowire, helping to stabilize a remanence mono-domain magnetic state (see example 2 for more details). Stabilization of the mono-domain state after the nanowires have been magnetized parallel to their long axis entails a remanence magnetization value of between 60-100% of the saturation magnetization value, since the magnetization of the wire remains mostly aligned with its axis in the absence of an external magnetic field.
    [0172] The magnetic remanence values corresponding to the nanowires have been determined according to their diameter (Table 1), concluding that diameters less than 50 nm are necessary to stabilize the mono-domain state. The 30nm nanowires, with their oxide coating of approximately 5nm, were the ones with the best properties, as they contained the largest fraction of mono-domain threads of all the samples studied.
    [0174] Figure 3 shows the magnetization curve versus applied field of the 30nm FeCo wires, in which a high ratio of remanence magnetization (Mr) to saturation magnetization (Ms) can be observed, which has the consequence that the nanowires they have a remanence of 102 Am2kg-1, measured on a vibrating sample magnetometer (VSM). Furthermore, it is observed how the saturation magnetization of the nanowires is relatively high, reaching 140 Am2 values. Kg-1, as a consequence of the limited thickness of the oxide layer of the coating (5 nm).
    [0175] Table 1
    [0177]
    [0180] Example 2. Magnet comprising FeCo soft magnetic nanowires
    [0181] This example demonstrates the improvement in magnetic performance, relative to the best commercial hard ferrites, of the biphasic compounds corresponding to the magnet of the present invention.
    [0183] Magnets were made with a composition of 60% by weight of hard magnetic strontium ferrite particles (SrFe ^ O ^) and 40% by weight of soft FeCo magnetic nanowires, 30 nm in diameter, obtained according to Example 1.
    [0185] The two materials in powder form were mixed in the presence of ethanol. The mixture is sonicated for one minute in an "ultrasons sonicator" equipment with a power of 50 W for 60 Hz and centrifuged for 1 min at 7000 rpm. A magnetic field of 0.2 T was applied during drying, also after After drying, the material was aligned using a 0.3 T magnetic field and compacted applying a pressure of 400 Kg.cm-2 housed inside a gelatin capsule using a spatula and a piece of cotton.
    [0187] Table 2 shows the properties of the different magnets of the invention manufactured Table 2
    [0189]
    [0192] The best results were obtained for magnets comprising 30nm gauge nanowires, where the magnetic monodomain state predominates.
    [0194] Comparative Data: Magnetic Properties of Ferrite Hard Magnetic Particles, FeCo Soft Magnetic Nanowires and the Magnets of the Present Invention
    [0196] Figure 4 shows the magnetization curves versus applied field of the hard magnetic particles of ferrite (1), of the soft magnetic nanowires of FeCo (N3), and of the magnet of the invention comprising 60% of hard magnetic particles of ferrite and 40% by weight of FeCo soft magnetic nanowires (I6).
    [0198] Figure 4 clearly shows the increase in the remanence magnetization of both the magnet of the invention and the FeCo soft magnetic nanowires which is 87 Am2.kg-1 for a generated field of 0.68 T, greater than the Magnetization of the hard magnetic particles of commercial ferrite. It should be noted that the best commercial ferrites generate fields of 0.45 T. The coercive field of the magnet of the Invention is 1047 Oe.
    [0200] Comparative data Magnet comprising Fe metallic spherical soft magnetic particles
    [0202] Example 3 shows a magnet composed of hard magnetic particles of ferrite (80% by weight) and soft magnetic particles in the form of spherical Fe nanoparticles with an average diameter of 25 nm (20% by weight). Figure 5 shows the magnetization curves of the magnet.
    [0204] Table 3
    [0206]
    [0209] Table 4 shows the properties of the different magnets of the invention manufactured
    [0210] The remanence magnetization for the ferrite was 63 Am2.kg-1 while the magnet has a remanence magnetization of the I7-I12 magnets was a maximum of 55 Am2.kg-1.
    [0211] Table 4
    [0213]
    [0216] The values obtained from the remanence magnetization for the I7-I12 magnets are justified by the multi-domain state of the Fe spherical soft magnetic nanoparticles.
    [0218] The remanence magnetization values and the remanence / saturation ratio are clearly lower than the values obtained for the I1-I6 magnets of the present invention, which include soft magnetic nanowires, especially in the case of 30nm nanowires that are at monodomain status.
    [0220] An advantageous aspect of the present invention results in that the mechanism involved in obtaining the permanent magnet of the present invention allows to solve the negative effect that agglomerates of anisotropic particles of metallic material have with a soft magnetic response in the improvement of energy products. magnetic. Agglomerates of soft magnetic particles constitute in themselves a multi-domain system and the difficulty in dispersing these particles it prevents effective coupling from occurring between the particles corresponding to the hard and soft magnetic phases. In the magnet of the present invention, magnetically soft particles with an aspect ratio sufficient to preserve their magnetic monodomain status are used. The oxide layer of the nanowire coating, in addition to limiting the oxidation degradation processes of said particles, is also beneficial in modifying the surface charge state of the nanowires. Said surface modification translates into an alteration of the short-range forces on the surface that are responsible for the accumulation of surface charge. The amorphous nature of the oxide layer of the coating is likewise beneficial, since the absence of crystalline order minimizes the energy of surface dipole interactions by reducing the agglomeration of the soft magnetic particles of the present invention.
    [0222] Comparative data: Computational simulation of the aspect ratio that stabilizes the magnetic mono-domain state in the magnet
    [0224] In this example, the minimum aspect ratio value that stabilizes the magnetic mono-domain state of the nanowires is established, by means of micromagnetic simulations of their domain structure.
    [0226] Figure 6 shows the spin structure of a nanowire 30 nm in diameter and 100 nm in height, that is, with an aspect ratio R = 3. In the central part of the nanowire, the spins aligned with the long axis are observed. of the nanowire and therefore would contribute to the remanence by being oriented in the magnet. The fraction of spins aligned with the axis is 83%. At the ends of the wire, however, it is observed how the spins deviate from the direction parallel to that determined by the length of the wire in order to minimize the accumulation of magnetic poles.
    [0228] Figure 7 shows the evolution of the coercive field (Hc) and the remanence to saturation ratio (Mr / Ms) with the length of the wire, for a nanowire of 30 nm in diameter. The increase in both values is related to the transition from a multidomain state to a monodomain state that occurs with increasing aspect ratio. This effect is due to the fact that to reverse the magnetization it is necessary to overcome the anisotropy of form, which is maximized with the increase in the length of the nanowire and in particular with the increase in the aspect ratio. It is observed that the value of Coercive field increased until it was close to saturation for a length around 150 nm, corresponding to an aspect ratio of n = 3, and in saturation for n> 5.
    [0230] The transition to the multidomain state occurs by increasing the diameter or gauge of the nanowires, that is, by reducing the aspect ratio. In soft anisotropic or nanowire magnetic structures, a competition occurs between magnetocrystalline anisotropy, which favors the alignment of the magnetization along a preferred crystallographic axis, and anisotropy in a way that aims to avoid the accumulation of magnetic poles. The expression for shape anisotropy, Ks, is:
    [0232] Ks = 1/2. Nd. More
    [0234] where Ms is the saturation magnetization of the material and Nd is its deterrent factor. The deterrent factor of a nanowire is defined as
    [0236] Nd = 1 / (2n + 1)
    [0238] where n is the aspect ratio.
    [0240] Simulations carried out for metal alloy particles (Fe, FeNi, FeCo), show that shape anisotropy dominates, that is, it is greater than magnetocrystalline, for aspect ratios n> 3. For aspect ratios n> 5, more than 90% of the nanowire spins are aligned with its axis. Therefore, this value is established as the one necessary to stabilize a robust mono-domain state.
    权利要求:
    Claims (14)
    [1]
    1. Permanent magnet, characterized by comprising
    • Hard magnetic particles with diameters between 100 nm and 100 pm and of ferrite or hexaferrite composition of the formula MeFe ^ O 19 , where Me is a divalent alkaline earth metal selected from Sr + 2, Ba + 2 and any of its combinations;
    • A soft magnetic structure with an aspect ratio greater than or equal to 3 and with a monodomain magnetic structure,
    or of a composition selected from Fe, Co, a Fe alloy, a Co alloy, a FeCo alloy, a FeNi alloy, a FeSiB alloy or a combination of the above,
    or that it is passivated with an amorphous surface oxide layer with a thickness less than or equal to 10 nm,
    or where the weight percentage of the soft magnetic structure is between 1% and 40% with respect to the final weight of the magnet,
    where the hard magnetic particles and the soft magnetic structure are magnetically oriented in the same direction.
    [2]
    2. Permanent magnet according to claim 1, wherein the percentage of hard magnetic particles is greater than or equal to 60% by weight with respect to the final weight of the magnet.
    [3]
    3. Permanent magnet according to any of claims 1 or 2, wherein the soft magnetic structure has an aspect ratio greater than or equal to 5.
    [4]
    4. Permanent magnet according to any of claims 1 to 3, wherein the soft magnetic structure is a wire with a length of between 150 nm and 60 pm and a gauge less than or equal to 100 nm.5
    [5]
    5. Permanent magnet according to claim 4, wherein the soft magnetic structure is a wire with a gauge of less than 50 nm.
    [6]
    6. Permanent magnet according to any of claims 1 to 5, wherein the amorphous surface oxide layer with mono-domain structure has a thickness of less than 5 nm.
    [7]
    7. Procedure for obtaining a permanent magnet according to any of claims 1 to 7, characterized in that it comprises the following steps:
    a) electrodeposition of soft magnetic structure in the presence of a porous membrane, where the pores of the membrane correspond to the dimensions of the soft magnetic structure,
    b) removal of the porous membrane by dissolution,
    c) drying the soft magnetic structure obtained in step (b) at a temperature of between 30 ° C and 120 ° C and in the presence of an air atmosphere,
    d) Ultrasound mixing of the soft magnetic structure obtained in step (c) with the hard magnetic particles in a liquid medium until obtaining a homogeneous mixture, and
    e) drying and compacting the product obtained in step (d) in the presence of a magnet of between 0.20 T and 1.25 T and under a pressure of between 150 Kg / cm2 and 1500 Kg / cm2.
    [8]
    The method according to claim 7, wherein the porous membrane of step (a) has transverse pores, where each of the pores has a diameter of between 10 nm and 300 nm, a pore length greater than or equal to 100 pm and a pore density of between 105 to 109 pores per cm2.
    [9]
    9. The process according to any of claims 7 or 8, wherein the porous membrane of step (a) is polymer based or an oxide.
    [10]
    The process according to any of claims 7 to 9, wherein the drying of step (e) is carried out by heat treatment in an oven at a temperature of between 30 ° C and 120 ° C and in the presence of an atmosphere of air.
    [11]
    11. The process according to any of claims 7 to 10, wherein the drying carried out in step (d) is partial and complete.
    [12]
    12. Use of the magnet according to any of claims 1 to 6, as part of a generator.
    [13]
    13. Use according to claim 12, wherein the generator is selected from an electric turbine generator, a flywheel and a wave generator.
    [14]
    14. Use of the magnet according to any of claims 1 to 6, as part of a motor vehicle.
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    同族专利:
    公开号 | 公开日
    WO2020128126A1|2020-06-25|
    ES2768433B2|2020-11-13|
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    PCT/ES2019/070848| WO2020128126A1|2018-12-20|2019-12-16|Permanent magnet, method for obtaining same and uses|
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