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    • 专利摘要:
    Procedure for obtaining a dense, magnetically anisotropic ceramic permanent magnet. The present invention relates to a process for obtaining a permanent ceramic magnet that comprises a step of mixing hard or soft magnetic micro- and/or nanoparticles with a basic or acidic organic solvent, a compaction step, a step of heating under pressure, a cooling stage and a sintering stage. 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:ES2848873A1
    申请号:ES202030112
    申请日:2020-02-11
    公开日:2021-08-12
    发明作者:Rubio Aida Serrano；Martin Eduardo Garcia；Lozano Jose Francisco Fernandez；Miralles Cecilia Pilar Granados；Michelena Adrian Quesada
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

    [0002] Procedure for obtaining a dense and magnetically anisotropic ceramic permanent magnet
    [0004] The present invention relates to a process for obtaining a permanent ceramic magnet that comprises a step of mixing hard or soft magnetic micro- and / or nanoparticles with a basic or acidic organic solvent, a compaction step, a step of heating under pressure, a cooling stage and a sintering stage.
    [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 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 at an industrial level are based on rare earths, however, the global crisis associated with these elements has highlighted the economic, geostrategic and environmental importance of preparing alternative magnets with competitive performance for certain applications that allow to reduce the rare earth dependence.
    [0014] One way to reduce the rare earth content in permanent magnets is to combine a hard magnetic material based on rare earths and a hard magnetic material based on ferrites of an oxidic nature, without worsening or maintaining their magnetic properties, as claimed by CN106312077.
    [0016] CN105006325 discloses a method for preparing compound ferrite powder with 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 method adopted, the coupling effect of Exchange can be done without the need for high temperature sintering. However, the resulting product does not exhibit permanent magnet behavior since it exhibits soft magnetic behavior with remanent magnetization values lower than 0.12T.
    [0018] CN101481241 refers to a method for the preparation of magnetic nanocrystalline particles, characterized in that an aluminum-doped barium ferrite nanocrystalline powder exhibiting hard magnetic behavior and a nickel-copper-zinc ferrite nanocrystalline powder with soft magnetic behavior are they are mixed, dried and heat treated, obtaining a complex nanocrystalline phase that has a saturation magnetization of 50 emu-g-1, and a coercive field of 5.8 kOe.
    [0020] WO2017137640A1 claims hybrid permanent magnet microcomposites comprising an oxide-based ferrite hard magnetic material, a metal-based soft magnetic material and an organic coupling agent. The microcomposite presents improvements of 25% in remanence magnetization with respect to the ferrite phase, of isotropic powders without magnetically oriented. In the production process, 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 material of WO2017137640A1 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 (i.e. magnetically oriented) materials. In this way, although the isotropic composite has a greater remanence, it does not necessarily imply that said improvement can be transferred to a magnetically oriented or anisotropic composite.
    [0022] Permanent magnets are usually sintered at high temperatures in order to obtain dense bodies and maximize the volume-dependent energy product. A dense magnetic material also has the advantage of its mechanical integrity and greater resistance to environmental degradation processes. The densification or sintering processes take place at high temperatures, which in the case of ferrite magnets require temperatures> 1200 ° C and times greater than 30 min to 4 hours at maximum temperature. During heat treatment, grain growth occurs as a consequence of mass transport phenomena. The consequence of the increase in grain size is a reduction in the magnetic response, in particular a strong reduction in the coercive field, He.
    [0023] US2017 / 0088471A1 claims the sintering of ceramic and composite materials with at least one inorganic element by the cold sintering method called "coid sintering process". This methodology allows sintering at least one inorganic compound in particulate form by using an aqueous based solvent of at least 50% by weight of H20. The use of this aqueous solvent in a proportion not greater than 30% by weight with respect to the inorganic component partially solubilizes the inorganic compound to give rise to a densified material at temperatures below 2000C and applying a uniaxial pressure of less than 5000 MPa. As a result of the cold sintering process, densified parts with at least a relative density of 85% can be obtained. However, this process limits the controlled grain growth of the particles.
    [0025] Therefore, it is necessary to develop new procedures for obtaining competitive permanent magnets that include minimal amounts of rare earths.
    [0027] DESCRIPTION OF THE INVENTION
    [0029] The following are definitions of certain terms that will be used throughout the description:
    [0031] By the term "hard magnetic particles" it is understood, in the present invention, as that particle that has a coercive field between 1.8 kOe and 2.5 kOe and a saturation magnetization between 40 emu / g and 65 emu / g. Said values were determined by means of a vibrating sample magnetometer for a maximum magnetic field of 1.1 T. These measurement conditions were maintained in all the examples of the present invention.
    [0033] By the term "soft magnetic particles" is understood in the present invention as that particle that exhibits a saturation magnetization comprised between 70 emu / g and 210 emu / g.
    [0035] In the present invention the term "organic solvent" encompasses both acidic and basic organic compounds. The most common organic acids are carboxylic acids, whose acidity is associated with their carboxyl group -COOH. Sulfonic acids, which contain the -SO 2 OH group, are relatively stronger acids. Alcohols, with OH, they can act like acids, but they are generally very weak. The relative stability of the acid conjugate base determines its acidity. Other groups can also confer acidity, generally weak: the thiol group -SH, the enol group, and the phenol group. In biological systems, the organic compounds that contain these groups are generally called organic acids.
    [0037] An organic base is an organic compound that acts as a base. Organic bases are generally, but not always, proton acceptors. They generally contain nitrogen atoms, which can be easily protonated. Amines and nitrogen-containing heterocyclic compounds are organic bases. Examples include: pyridine, alkanamines, such as methylamine, imidazole, benzimidazole, histidine, guanidine, phosphazene bases, hydroxides of quaternary ammonium cations, or some other organic cations.
    [0039] By the term "magnetic anisotropy" is understood as the inhomogeneity of the magnetic properties when measured in different directions of space. That is, the magnetic response is different depending on the direction in which it is examined.
    [0041] By the term "magnetocrystalline anisotropy" is meant the inhomogeneity of the magnetic properties along the examined axes of the crystal structure. A material will be magnetically harder the greater its total magnetocrystalline anisotropy.
    [0043] By the term "shape anisotropy" is understood the magnetic response as a consequence of the geometric shape of the material or of the particles that constitute it.
    [0045] The equivalences between magnetic units are 1 T = 10,000 G = 10,000 Oe = 795,775 kA-m-1 and 1 emu-g-1 = 4n-10'7 A m 2 kg-1
    [0047] Density or absolute density is the magnitude that expresses the relationship between the mass and the volume of a substance or a solid object. Its unit in the International System is kilogram per cubic meter (kg / m3), although it is often also expressed in g / cm3.
    [0049] The relative density of a substance is the relationship between its density and that of another reference substance; consequently, it is a dimensionless quantity (without units).
    [0050] In the present invention, the term "relative or apparent density" is understood as that relationship between the measured density and the theoretical density of a magnet.
    [0052] The present invention relates to a process for obtaining a ceramic permanent magnet that does not contain rare earths, is magnetically anisotropic and exhibits a bulk density greater than 90%. Said process is characterized in that it comprises a stage of mixing hard magnetic microparticles with a basic or acidic organic solvent, a heating stage under pressure, a cooling stage and a sintering stage.
    [0054] The ceramic permanent magnet obtained following the process of the present invention has a coercive field greater than 2400 Oe, for some preferred embodiments permanent magnets with a coercive field of up to 3000 Oe have been obtained.
    [0056] The main applications of said permanent magnets are framed within the sector of generation and storage of renewable energies (wind turbine generators, generators in wave parks, flywheels) and the automotive industry (a car contains an average of 400 magnets), for example magnets for power steering and electric windows, and in particular alternators and motors for electric or hybrid vehicles. In this sense, the new electric motors require the use of permanent magnets that withstand high temperatures with high energy products that require high coercive field values as claimed in the present invention, an aspect that will expand the use of these materials.
    [0058] The detailed description of the invention is presented below:
    [0060] In a first aspect, the present invention relates to a method for obtaining a ceramic permanent magnet comprising
    [0061] • hard magnetic particles in the form of platelets with a ferrite or hexaferrite composition of the formula MFei20ig, where M is a divalent alkaline earth metal selected from among Sr + 2, Ba + 2 and any of their combinations, and where said magnetic particles have a size distribution bimodal particle with a first particle size between 101 nm and 500 nm and a second particle size between 1 pm and 10 pm,
    [0062] characterized by comprising the following stages:
    [0063] a) mix homogeneously
    [0064] • hard magnetic particles with a ferrite or hexaferrite composition of the formula MFei20i9, where M is a divalent alkaline earth metal selected from among Sr + 2, Ba + 2 and any of their combinations, with a particle size between 101 nm and 10 pm,
    [0065] • and an organic solvent;
    [0066] where the percentage of the organic solvent ranges from 5% to 50% by weight with respect to the total weight of the mixture,
    [0067] b) compacting the homogeneous mixture obtained in step (a) at a uniaxial pressure of between 5 MPa and 360 MPa for a period of time between 6 s and 5 min;
    [0068] c) heating the product obtained in step b) under uniaxial pressure between 20 MPa and 5000 MPa at a temperature between 1200C and 3000C, and for a period of time between 30 min and 4h;
    [0069] d) cooling the product obtained in step (c) until reaching a temperature between 80 and 120 ° C to facilitate the extraction of the compacts, and subsequent cooling to room temperature between 18 ° C and 400 ° C;
    [0070] and e) sintering the product obtained in step (d) at a temperature between 10,000 ° C and 1150 ° C in the presence of an air atmosphere.
    [0072] Step (a) of the process of the present invention refers to homogeneously mixing
    [0073] • hard magnetic particles with a ferrite or hexaferrite composition of the formula MFei20i9, where M is a divalent alkaline earth metal selected from among Sr + 2, Ba + 2 and any of their combinations, with a particle size between 101 nm and 10pm
    [0074] • and an organic solvent;
    [0076] Said mixing process of step (a) is simple and low cost.
    [0078] The mixture is preferably carried out in an agate mortar, until the powder is homogeneously moistened by the acidic or basic organic solvent. In a scaling of the process the mixture is carried out in an intensive mixer type Eirich until the required degree of homogeneity is achieved.
    [0080] In a preferred embodiment of the process of the present invention, the mixture of step (a) further comprises
    [0081] • hard magnetic particles with a ferrite or hexaferrite composition of the formula MFei 2 0 i 9 , where M is a divalent alkaline earth metal selected from Sr + 2, Ba +2 and any of their combinations, with a particle size between 5 nm and
    [0082] 100 nm,
    [0083] you get a permanent magnet with a coercive field of up to 2800 Oe.
    [0085] In another preferred embodiment of the process of the present invention, the mixture of step (a) further comprises
    [0086] • soft magnetic particles of Fe or Fe 3 Ü 4 selected from particles of particle size between 10 pm and 15 pm or particles of particle size between 5nm and 100nm,
    [0087] obtaining a permanent magnet with a coercive field of up to 3000 Oe.
    [0089] In a preferred embodiment of the process of the present invention, step (a) is carried out in the presence of an atmosphere of the same acidic or basic organic solvent used in the mixture.
    [0091] Preferably, the hard magnetic ferrite nanoparticles / microparticles and the soft magnetic nanoparticles / microparticles are premixed, for example, by a dry milling process for 10 minutes in a Mixermill 8000 using a nylon container and zirconia balls stabilized with yttria of 1 mm in diameter, to obtain a homogeneous mixture of powders.
    [0093] In a preferred embodiment of the process of the present invention, the organic solvent of step (a) is an acidic organic solvent selected from glacial acetic acid (CH 3 COOH), oleic acid (C 18 H 34 O 2 ), lactic acid ( C 3 H 6 O 3 ), formic acid (CH 2 O 2 ), citric acid (CeHsO ), Oxalic acid (C 2 H 2 O 4 ), uric acid (C 5 H 4 N 4 O) or malic acid ( C 4 H 6 O 5 ); or a combination thereof.
    [0094] In a preferred embodiment of the process of the present invention, the organic solvent of step (a) is a basic organic solvent selected from anisole (C 7 H 8 O), aniline (C 6 H 7 N), purine (C 5 H 4 N 4 ), triethylamine (C 6 H 15 N), oleamine (C 18 H 37 N); or a combination thereof.
    [0096] Step (b) of the procedure refers to compacting the homogeneous mixture obtained in step (a) with a uniaxial pressure of between 5 MPa and 360 MPa, for a period of time between 6s and 5 min, at room temperature between 18 Cy400C.
    [0098] Said compaction stage (b) is industrially feasible.
    [0100] The compaction stage (b) is carried out in a period of time between 6 s and 5 min. This period of time ensures the alignment of the magnetic particles in the pressing direction to thus obtain an anisotropic magnetic material.
    [0102] In another preferred embodiment of the process of the present invention, compaction step (b) is carried out in the presence of a magnetic field of at least 0.2 T oriented in the direction perpendicular to the direction of the pressure exerted. The applied magnetic field is between 0.2T and 5 T.
    [0104] On the one hand, the application of an external magnetic field in the pressure application direction during the compaction process allows the hard magnetic particles with platelet morphology to be magnetically aligned along their magnetization axis, which due to their magnetocrystalline anisotropy is perpendicular to the plane of the platelets. On the other hand, the presence of an acidic or basic organic solvent during the application of a magnetic field reduces the friction between the particles and favors the alignment processes of the easy axis of magnetization of the hard magnetic particles and the external magnetic field applied.
    [0106] Stage c) of the process of the present invention refers to heating the product obtained in stage b) under uniaxial pressure between 20 MPa and 5000 MPa to the boiling temperature of the organic solvent used in stage (a), preferably at a temperature between 1200C and 3000C, for a time between 30 min and 4h.
    [0108] Pressure and temperature provide an increase in the density of the product obtained in step b) and exerts localized pressure between the particles that is concentrated in the areas of contact between them. The solubility of the strontium ferrite with the organic solvent used gives rise to a partial solubilization of the crystalline structure that takes place on the surface of the inorganic particles, preferably in the areas of greater chemical potential and / or in the areas where they accumulate. mechanical stresses. The process of partial solubilization of the magnetic structure thus allows a mass transport that favors the creation of sintering necks between the particles. This process is favored by a supersaturation of the solution that is accentuated with the elimination by evaporation of the organic solvent with the temperature.
    [0110] By way of comparison, comment here that pressure and temperature can cause a degradation of the hard magnetic condition that, generally, is partial after step (c) of the process of the present invention and results in amorphous phases or phases that do not present hard magnetic order at room temperature, such as a - Fe 2 Ü 3 . Said degradation is non-reversible by subsequent heat treatment when an aqueous-based acidic solution is used, that is, a solution in which the percentage by weight of water is greater than 50%.
    [0112] The product obtained in step (c) is allowed to cool to a temperature of between 80 and 1200C and with the help of a press applying uniaxial pressure it is extracted from the mold. The extraction of the compacted part is favored at said temperatures since the differences in the coefficient of thermal expansion values between the compacted part and the mold are less than those that occur when the assembly is cooled to room temperature. At room temperature, the metal mold exerts a maximum compression force on the compact and extraction is difficult. Subsequently, the product extracted from the mold is allowed to cool to room temperature, between 18 ° C and 40 ° C. After this stage (d) of the process of the present invention, pieces are obtained with a relative density greater than 70% with respect to the theoretical density.
    [0114] In the present invention, the term "relative or apparent density" is understood as that relationship between the measured density of the ceramic permanent magnet according to the Archimedean method or by the relationship between the mass determined by weighing and its volume determined by dimensional measurements. the theoretical density of hard magnetic particles of composition ferrite or hexaferrite of formula MFe ^ Oig, where M is a divalent alkaline earth metal selected from Sr + 2, Ba + 2 and any of their combinations.
    [0116] Note that the theoretical density of SFO is 5.1 g / cm3, the theoretical density of a-Fe 2 Ü 3 is 5.26 g / cm3 and the theoretical density of Fe 3 Ü 4 is 5.175 g / cm3. In this specification the term relative density refers to the% density relative to the theoretical density of SFO. Said term is used both for SFO materials and for materials that initially comprise a proportion of iron in its oxidized or non-oxidized form.
    [0118] Step (e) of the process of the present invention refers to the sintering of the product obtained in step (d) by heat treatment at a temperature between 10,000C and 11500C in the presence of an air atmosphere. The purpose of this stage is to improve densification and, if necessary, recover the hard magnetic condition. The sintered pieces obtained after step (e) result in dense pieces with a relative density greater than 90% with respect to the theoretical density.
    [0120] In a preferred embodiment of the process of the present invention, the maximum temperature reached in step (e) of sintering, between 10000C and 11500C, is kept constant for a period of time between 30 min and 4h.
    [0122] In another preferred embodiment of the process of the present invention, sintering step (e) is carried out by means of a thermal cycle with a heating rate of between 0.5 ° C / min and 10 ° C / min. These speed conditions are preferred because they favor the removal of organic solvent residues present in the product and solid state chemistry reactions to recover the hard magnetic phase.
    [0124] Throughout the description and claims the word "comprise" 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 characteristics 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.
    [0125] BRIEF DESCRIPTION OF THE FIGURES
    [0127] FIG. 1. Images by means of scanning electron microscopy of A) SFO powder used from the start, B) sintered by conventional thermal sintering after heat treatment for 4 h at 1100 ° C (M2) and C) sintered by conventional heat sintering after heat treatment during 4 h at 13000C (M5).
    [0129] FIG. 2. A) X-ray diffraction patterns obtained from SFO sintered by conventional thermal sintering at 11000C (M2) and 13000C (M5) for 4 h and B) Raman spectroscopy curves obtained from SFO sintered by conventional thermal sintering at 11000C (M2) and 13000C (M5) for 4 h. The Raman vibrational modes are assigned in the figure.
    [0131] FIG. 3. Magnetization versus applied field curves of conventionally sintered strontium ferrite magnets at a temperature of 10500C (M1), 11000C (M2), 11500C (M3), 12000C (M4) and 12500C (M5) for 4 h.
    [0133] FIG. 4. Magnetization curves versus applied field of SFO ferrite magnets sintered by cold sintering using (A) 1M acetic acid (M6) and after heat treatment at 11000C for 2 h (M7), (B) 17.5M of acetic acid (M8) and after heat treatment at 1100 ° C for 2 h (M9).
    [0135] FIG. 5. Magnetization versus applied field curves of conventionally sintered SFO ferrite magnets using glacial acetic acid (M10), oleic acid (M11) and oleamine (M12).
    [0137] FIG. 6. Images by means of scanning electron microscopy of (A) Magnet (M13) and (B) after a thermal treatment at 11000C for 2h Magnet (M14).
    [0139] FIG. 7. (A) X-ray diffraction patterns and (B) Raman spectroscopy curves obtained from Magnet (M13) and Magnet (M14). The Raman vibrational modes are assigned in the figure.
    [0141] FIG. 8. Magnetization curves versus applied field of (A) Magnet (M13) and after heat treatment at 11000C for 2h Magnet (M14), (B) Magnets (M14, M16, M18).
    [0142] FIG. 9. Magnetization curve versus applied field of magnet M19.
    [0144] FIG. 10. Images by means of scanning electron microscopy of (A) Magnet (M20) and (B) after a thermal treatment of 11000C for 2 h Magnet (M21).
    [0146] FIG. 11. Magnetization curves versus applied field of (A) Magnet (M20) and after a heat treatment of 1100 ° C for 2 h (M21), (B) Magnet (M22) and after a heat treatment of 11000C for 2 h ( M23).
    [0148] FIG. 12. Scanning electron microscopy images of (A) 10% mFe (M24), (C) 5% nFe (M26), (E) 10% nFe304 (M28), and after a heat treatment at 1100 ° C for 2 h: (B) +10% mFe (M25), (D) 5% nFe (M27), (F) 10% nFe304 (M29).
    [0150] FIG. 13. (A) X-ray diffraction patterns for magnets M24 to M29 and (B) Raman spectroscopy curves obtained for magnets for samples M24 to M29. The Raman vibrational modes are assigned in the figure.
    [0152] FIG. 14. Magnetization versus applied field curves of (A) Magnet M24 / M25, (B) M26 / 27 and (C) M28 / M29.
    [0154] EXAMPLES
    [0156] The invention will be illustrated below by means of tests carried out by the inventors, which show the effectiveness of the product of the invention.
    [0158] In order to show the advantages of the materials obtained in the present invention, two comparative examples related to a conventional sintering process and a cold sintering process are presented. Likewise, the conventional sintering process has been carried out using an organic solvent in the compaction stage since it is favorable for the mechanical orientation of the particles in obtaining compacts due to its morphology.
    [0160] By the term "sintering by the conventional method" is meant the sintering of parts obtained from powders previously compacted by heat treatment to achieve a final density greater than 90% of the theoretical density of the material. In a conventional sintering process the mass transport responsible for densification is thermally activated requiring elevated temperatures.
    [0162] By the term "cold sintering" is meant the sintering of parts obtained from powders and an aqueous solution by means of a combined process of temperature up to 2000C and pressure. In a cold sintering process, the mass transport responsible for densification occurs through supersaturation of the aqueous solution by removing the solvent with temperature and in the presence of high pressures to achieve a final density greater than 85% of the theoretical density. of the material.
    [0164] In the comparative examples and in the examples of the present invention, the same starting powder of strontium hexaferrite or strontium ferrite, SFO, is used in order to show the advantages of the process followed in the present invention.
    [0166] Comparative Example 1. Manufacture of a Strontium Hexaferrite (SFO) Permanent Magnet by Conventional Thermal Sintering
    [0168] To prepare a ceramic permanent magnet, we started from platelet-shaped strontium hexaferrite (SFO) particles that presented a bimodal particle size distribution, whose two contributions correspond to platelet thicknesses between 100 nm and 500 nm and diameters of Platelet between 1 pm and 5 pm. 0.5 g of the particles in powder form were homogenized by hand in an agate mortar for 5 minutes. Figure 1A shows the morphology of the starting particles by means of scanning electron microscopy.
    [0170] In a second stage, the homogeneous powder was compacted in a stainless steel die with an internal diameter of 0.83 cm and a pressure of 150 MPa was applied for 5 minutes.
    [0172] Subsequently, the compacted pieces were extracted and the conventional thermal sintering of the samples was carried out at a maximum temperature of: 1050 0C (M1), 1100 0C (M2), 1150 0C (M3), 1200 0C (M4) and 1250 0C ( M5). The heat treatment was carried out in an air atmosphere and with a heating rate of 5 ° C / min until reaching the maximum temperature where it was maintained for 4 h and the subsequent cooling to room temperature according to the oven.
    [0173] Figures 1B and 1C show the scanning electron microscopy images of a magnet sintered by conventional sintering at a sintering temperature of 11000C (M2) and 12500C (M5) respectively, compared to the starting strontium ferrite powder ( Figure 1A). In both sintered pieces an increase in grain size is obtained with respect to the particle size of the starting material. During the thermal process, sintering necks occur between the particles and, where appropriate, an increase in the density of the piece when increasing the maximum temperature of the process, as shown in Table 1. Specifically, relative densities of 74 were obtained. % with respect to the theoretical density for sample M2 and 98% with respect to the theoretical density of SFO for sample M5. The grain size of the ferrite magnets showed growth with respect to the average starting particle size, becoming an average of 2 pm for the M2 magnet and 8 pm for the M5 magnet. In the latter case, grains with sizes greater than 50 pm were observed. The data relative to the M1-M5 magnets sintered by the conventional method, and the compact one before heat treatment (M0) are summarized in Table 1.
    [0175] Table 1. Characteristic properties of permanent magnets prepared by conventional sintering.
    [0177]
    [0180] * Regarding the theoretical density of SFO
    [0181] Figure 2A shows the diffraction patterns obtained by X-ray diffraction, using a Bruker D8 equipment with radiation at Cu Ka (A = 0.154 nm), of the samples sintered by conventional thermal sintering at temperatures of 1100 0C (M2) and 1250 ° C (M5). Both pieces show diffraction patterns in which the Bragg peaks corresponding to strontium ferrite are identified. By treating the data obtained by X-ray diffraction from a Rietveld refinement, it was identified that the crystalline phase in both samples is made up of 100% strontium ferrite.
    [0183] Figure 2B represents the results obtained by confocal Raman spectroscopy, using a Witec ALPHA 300RA with a Nd: YAG laser (532 nm). The Raman spectra corroborate the data obtained by X-ray diffraction presented in Figure 2A, showing a Raman spectrum corresponding to strontium ferrite, identifying the main modes of vibration and without the presence of other phases.
    [0185] The magnetic response of the magnets M1, M2, M3, M4 and M5 is represented in figure 3. M1 has a coercive field of 2.8 kOe, a ratio of remanence magnetization versus saturation magnetization of 0.65 . Note that a randomly oriented material would have a ratio of 0.5 and that a fully oriented material would achieve a ratio of 1.0 and a saturation magnetization of 45.4 emu / g. It is presently found therefore that a slight orientation of the SFO particles occurs during the pressing stage due to mechanical effects related to the morphology of the platelet-shaped particles.
    [0187] The observed magnetic response is associated with a characteristic magnetic hysteresis cycle of a hard material, with improved magnetic characteristics with respect to the compacted non-sintered starting SFO material (M0). As we increase the sintering temperature, the magnetic properties are affected by decreasing the coercive field to 2.5 kOe for M2 and 2.0 kOe for M3. In both M1, M2 and M3, their low density did not provide sufficient mechanical integrity due to low densification to handle the samples properly. For M4, although the relative density compared to the theoretical one improves to have a value of 94%, a drastic decrease in the magnetic response was obtained with a decrease in the coercive field to 1.3 kOe. Magnetic response that decreases with increasing sintering temperature to 12500C (M5), having a coercive field of 1.0 kOe, with a reduction in the ratio between magnetization of remanence against saturation magnetization at 0.55. This worsening of the magnetic response is related to the increase in grain size (figure 1) associated with the densification of the magnet.
    [0189] Therefore, from strontium ferrite particles, obtaining a densified permanent magnet by conventional heat treatment is associated with an increase in the grain size that reduces its magnetic response, in particles the coercive field that decreases by an amount greater than 50 % with respect to the value of the initial dust particles.
    [0191] Comparative Example 2. Obtaining a permanent magnet of strontium hexaferrite (SFO) by cold sintering using an aqueous solution according to US2017 / 0088471A1
    [0193] A mixture was prepared based on the strontium hexaferrite particles obtained in comparative example 1, corresponding to 0.5 g of SFO particles and 30% by weight of 1 M or 17.5 M acetic acid as aqueous-based solvent. . The mixture was homogenized by hand in an agate mortar for about 10 minutes until reaching a wetted powder.
    [0195] In a second stage, the wetted mixture was compacted in a tempered steel die with an internal diameter of 0.83 cm at a pressure of 150MPa for 5 minutes.
    [0197] Subsequently, the whole of the die with the compacted wetted powder was subjected to a heating process by means of a heating press in an air atmosphere, keeping the sample under pressure. This process of heating under pressure is referred to in the literature as "cold sintering". The process conditions were at a temperature of 190 ° C for 2 h under a uniaxial pressure of 375 MPa. After the process, the piece was extracted from the die at a temperature of 80 ° C and subsequently cooled under ambient conditions to room temperature. The magnets thus obtained are named M6 and M8 using 1 Mo17.5M acetic acid respectively.
    [0199] In a further process, the magnets were subjected to a heat treatment at a temperature of 11000 ° C for 2 h in an air atmosphere with a heating rate of 5 ° C / min. The resulting magnets after heat treatment are called M7 and M9 magnet using 1 Mo17.5M acetic acid respectively.
    [0201] The M6 magnet reached a relative density <80% with respect to the theoretical density and presented a percentage of crystalline phases of 79% SFO and 21% of Fe 30 4 phase iron oxide. After heat treatment at 11000C for 2 hours, the M7 magnet presented a density of 84% with respect to the theoretical density with a decrease in the percentage of iron oxide Fe304 to 10%. Increasing the molarity of the aqueous solution from 1M to 17.5 M, the magnet obtained M8 presented a density of 80% with respect to the theoretical density with a percentage of crystalline phases of 74% SFO and 26% of iron oxide a- Fe303, while after heat treatment at 1100 ° C for 2 hours, the M9 magnet increased relative density to 88% with a decrease in the percentage of a-Fe303 to 8%. In both cases, the process led to a partial recrystallization of the ferrite and a densification of the part after heat treatment at high temperature.
    [0203] The magnetic response of M6, M7, M8 and M9 is represented in figure 4. M6 and M8 presented a coercive field of 1.6 kOe and a ratio of remanence magnetization versus saturation magnetization of 0.58 and 0. , 62 respectively indicating that the mechanical orientation of the platelet morphology particles did not improve with respect to the samples obtained in comparative example 1. The observed magnetic response is associated with a cycle of magnetic hysteresis characteristic of the combination of SFO and the oxide of corresponding iron. In both cases, for the M6 and M8 magnet, their low density did not provide sufficient mechanical integrity due to low densification to handle the sample properly.
    [0205] For the M7 and M9 magnets, after the heat treatment process at 11000C, an increase in the magnetic response was obtained by increasing both the coercive field to 2.7 kOe and 2.3 kOe respectively and the ratio between remanence magnetization vs. saturation magnetization at 0.69 for both magnets. This improvement in the magnetic signal is related to the partial recovery of the SFO phase and the retention of the particle size after the heat treatment process. However, the density of the permanent magnet is less than 90% of the theoretical density of SFO and presents water absorption and brittleness that prevent its use as a ceramic permanent magnet.
    [0207] Therefore, by cold sintering procedure or low heating pressure using an aqueous solvent did not reach a level of densification higher than 85%. In addition, a notable loss of magnetic properties is observed that correlates with the non-reversible chemical decomposition of the SFO hard magnetic phase to give rise to iron oxide phases. The subsequent heat treatment allows the recrystallization of the SFO phase that produces an improvement in the magnetic properties, however, the density of the ceramic material does not exceed 90% of the theoretical density of SFO.
    [0209] Table 2. Characteristic properties of permanent magnets prepared by cold sintering using an aqueous solution.
    [0211]
    [0214] * Regarding the theoretical density of SFO
    [0216] Comparative Example 3. Manufacture of Strontium Hexaferrite (SFO) Permanent Magnet by Conventional Thermal Sintering Using an Organic Solvent
    [0218] A mixture of 0.5 g of the particles obtained in comparative example 1 of strontium hexaferrite, SFO, and a certain percentage by weight of an organic solvent (glacial acetic acid, oleic acid or oleamine) was prepared. The mixture was homogenized by hand in an agate mortar for about 10 minutes until reaching a wetted powder.
    [0219] In a second stage the homogeneously wetted powder was compacted in a tempered steel die with an internal diameter of 0.83 cm and a pressure of 150 MPa was applied for 5 minutes.
    [0221] Subsequently, the compacted pieces were extracted and a conventional thermal sintering process of the samples was carried out at a maximum temperature of 1100 ° C for 2 h. The heat treatment was carried out in an air atmosphere using a heating rate of 5 ° C / min until reaching the maximum temperature where it was maintained for 2 hours and the subsequent cooling down to room temperature according to the oven.
    [0223] The data relative to the magnets using glacial acetic acid (M10), oleic acid (M11) and oleamine (M12) sintered by conventional thermal methodology are summarized in Table 3. The sintered pieces presented as the only crystalline phase, 100% SFO and reached a relative density compared to the theoretical SFO <80%, regardless of the organic solvent used for sintering.
    [0224] The magnetic response of M10, M11 and M12 is represented in figure 5. In all cases the magnets presented a coercive field> 2.9 kOe, a ratio of remanence magnetization versus saturation magnetization of around 0.70 and a saturation magnetization of 55 emu / g. The use of an organic solvent favored the mechanical alignment of the particles with platelet morphology of SFO compared to the processes that use an aqueous-based solvent. The observed magnetic response is associated with a characteristic magnetic hysteresis cycle of a hard material, with improved magnetic characteristics over compacted non-sintered SFO material (M0). However, in all cases, the density is less than 90% of the theoretical density and the mechanical integrity is insufficient for use as a sintered permanent magnet.
    [0226] Therefore, a conventional sintering process in which the compaction step is improved by the use of an organic solvent does not solve the problem of obtaining densified compacts with a coercive field equal to or greater than the coercive field of the starting SFO particles.
    [0228] Table 3. Characteristic properties of permanent magnets prepared by conventional sintering using an organic solvent.
    [0229]
    [0232] * Regarding the theoretical density of SFO
    [0234] Example 1. Obtaining a permanent magnet by the process of the present invention
    [0236] To prepare a ceramic permanent magnet, strontium hexaferrite (SFO) particles were used, the same powder described in comparative example 1 was used with a platelet shape that presented a bimodal particle size distribution corresponding to platelet thicknesses between 100 nm and 500 nm and platelet diameters between 1 pm and 5 pm.
    [0238] Mixtures were prepared comprising 0.5 g of SFO and the organic solvents listed in Table 4, which were glacial acetic acid, oleic acid or oleamine. The mixtures were homogenized by hand in an agate mortar for about 10 minutes until reaching a wetted powder.
    [0240] In a second stage, the wetted mixture resulting from the first step was compacted in a tempered steel die with an internal diameter of 0.83 cm at a pressure of 150 MPa for 5 minutes.
    [0242] Subsequently, the whole of the die with the compacted wetted powder was subjected to a heating process under pressure by means of a heating press in an air atmosphere. The conditions of the heating process under pressure with parameters relative to pressure, temperature and time are specified in Table 4. The pressure heating process temperature was selected above the decomposition temperature of the organic solvent. After the process, the piece was extracted from the die at a temperature of 80 ° C and subsequently cooled under ambient conditions. The resulting magnets are called M13, M15 and M17 magnet (See Table 4).
    [0244] In a subsequent process the magnets M13, M15 and M17 were subjected to a heat treatment at a maximum temperature of 11000C for 2 h in an air atmosphere. The heat treatment consisted of: a heating ramp of 5 ° C / min until reaching the maximum temperature where it was maintained for 2 h and subsequent cooling to room temperature according to the oven. The magnets thus obtained are called M14, M16 and M18 (See Table 4).
    [0246] Figure 6A shows the scanning electron microscopy micrograph of a sintered magnet using glacial acetic acid as an organic solvent at 50% by weight with respect to the SFO material, at a temperature of 1900C for 2 h under a uniaxial pressure of 375 MPa (magnet M13). The grain size of the M13 ferrite-based magnet exhibited a bimodal microstructure with grain sizes of approx. 2 pm and 5 pm respectively which is a reflection of the size distribution of the starting particles. During the process sintering necks are produced between the particles, obtaining a relative density with respect to the theoretical density of 85%. After heat treatment at 11000C for 2 hours (figure 6B), the M14 magnet presented a density of 92% with respect to the theoretical density, identifying a growth in particle size that maintains the bimodal microstructure and becomes approx. 3 pm and 5 pm.
    [0248] An analysis by X-ray diffraction from a Rietveld refinement determined a partial decomposition of SFO for sample M13 when using glacial acetic acid with a percentage of crystalline phases of 66% SFO and 34% iron oxide a-Fe 20 3 . After the heat treatment process at 1100 ° C, the sample M14 presented a total recrystallization of SFO, not identifying any impurity, neither crystalline nor amorphous, as shown in figure 7 (analysis performed by X-ray and Raman spectroscopy). Therefore, it is observed that the heat treatment allows to reach a suitable density and recrystallize the SFO phase to obtain a sintered ferrite permanent magnet material.
    [0249] The magnets prepared in the present invention using oleic acid (M15) and oleamine (M17) maintained the crystalline phase of SFO after the compaction process followed, and a low densification of 75% and 72% of the theoretical density of SFO respectively. After the heat treatment process at 11000C for 2 h the magnets M16 and M18 using oleic acid and oleamine respectively, reached adequate densification with relative density values> 92%.
    [0251] Table 4. Characteristic properties of the permanent magnets of the present invention using organic solvent
    [0253]
    [0254]
    [0257] * Regarding the theoretical density of SFO
    [0259] The magnetic response of M13, M15 and M17 show a coercive field of around 1.6 kOe and a ratio of remanence magnetization versus saturation magnetization of 0.64, 0.62 and 0.71 respectively. Its low density did not provide sufficient mechanical integrity to handle the sample properly.
    [0261] After heat treatment of the M13, M15 and M17 parts at 11000C for 2 h, the M14, M16 and M18 magnets presented a density of 92% with respect to the theoretical one, a coercive field of at least 2.9 kOe and an improvement in the ratio of the remanence magnetization versus saturation magnetization greater than 0.71. The improvement in the orientation of the particles combines the mechanical orientation during the compaction process and a preferential recrystallization during the treatment at 11000C. The magnetic response of magnets M13, M14, M16, and M18 is presented in Figure 8.
    [0263] The permanent magnets of the present invention therefore have the advantages of a density greater than 90% which provides them with adequate mechanical integrity for use as permanent ceramic ferrite magnets. The process of the invention allows to control the growth of the grain size and the crystalline phases of hard ferrite that provide a high coercive field. The properties of the permanent magnets of the present invention represent an improvement over conventional sintering processes (Comparative Example 1) and over cold sintering processes that use water-based solvents (Comparative Example 2) given that in the examples Comparative tests did not reach a similar degree of densification, keeping the grain size controlled. Likewise, in comparative examples 1 and 2, the magnetic properties for dense materials achieved by the process of the present invention are not achieved. It is demonstrated that the process of the present invention solves the problem of densifying permanent magnets by limiting the grain growth to provide an improved permanent magnet.
    [0265] Example 2. Obtaining a permanent magnet by the method of the invention in the presence of a magnetic field
    [0267] It starts with the precursor mixture used in the M17 sample, mixed manually in an agate mortar for about 10 minutes until reaching a homogeneous wetted powder.
    [0269] In a second stage, the wetted mixture resulting from the first step was compacted in a tempered steel die with an internal diameter of 1 cm at a pressure of 100 MPa, simultaneously applying a magnetic field of 0.3 T. Process prior to sintering.
    [0271] Subsequently, the die assembly with the compact was subjected to heating under pressure by means of a heating press in an air atmosphere. The process conditions were at a temperature of 260 ° C, above the boiling temperature of the organic solvent, for a time of 2 h under a uniaxial pressure of 460 MPa. After the process, the piece was extracted from the die at a temperature of 80 ° C and subsequently cooled to room temperature.
    [0273] In a subsequent process, the obtained magnets were subjected to a heat treatment at a maximum temperature of 11000C for 2 h in an air atmosphere. The thermal treatment consisted of heating at a rate of 5 ° C / min until reaching the maximum temperature where it was maintained for 2 h and subsequent cooling to room temperature. In this way, the M19 magnet was obtained, whose properties are presented in table 5.
    [0275] Table 5. Properties of an anisotropic permanent magnet of the present invention obtained by the process of the present invention.
    [0277]
    [0278]
    [0281] * Regarding the theoretical density of SFO
    [0283] The M19 magnet had a relative density with respect to the theoretical density of 92%. This relative density is similar to that obtained without applying a magnetic field during the previous compaction of the mixture (magnet M18).
    [0285] The magnetic response corresponding to the M19 magnet is shown in figure 9. A slight reduction of the coercive field was observed with respect to the M18 magnet, going from 3 kOe to 2.4 kOe. Additionally, an improvement in remanence magnetization is obtained compared to saturation magnetization, going from 0.73 for magnet M18 to 0.86 for magnet M19. The increase in said ratio indicates a greater degree of orientation of the crystalline structure in the pressing direction as a consequence of the orientation of the particles in the presence of the external magnetic field favored by the organic solvent, the mechanical action of the pressing process itself and the orientation crystalline during heat treatment. The M19 magnet of the present invention therefore has an anisotropic behavior.
    [0287] Example 3. Obtaining a permanent magnet from mixtures of microparticles and nanoparticles of strontium ferrite (SFO) by the method of the invention
    [0289] A mixture was prepared with 90% by weight of SFO, and 10% by weight of strontium hexaferrite nanoparticles, (hereinafter "nSFO"). The mixture was homogenized by means of a dry milling process for 10 min in a Mixermill 8000 equipment using a nylon container and yttria stabilized zirconia balls of 1 mm in diameter.
    [0291] From said mixture, the procedure described in Example 1 was followed, which comprised: a) homogeneous mixing of the previous SFO and nSFO mixture with an organic solvent of glacial acetic acid or oleic acid;
    [0292] b) compacting the homogeneous mixture obtained in step (a) at a uniaxial pressure of 200 MPa for a period of 5 min;
    [0293] c) heating the product obtained in step b) under uniaxial pressure between 20 MPa and 5000 MPa at a temperature between 1200C and 3000C, and for a period of time between 30 min and 4h;
    [0294] d) cooling the product obtained in step (c) until reaching a temperature between 80 and 120 ° C to facilitate the extraction of the compacts, and subsequent cooling to room temperature between 18 ° C and 400 ° C;
    [0295] and e) sintering the product obtained in step (d) at a temperature between 10,000 ° C and 1150 ° C in the presence of an air atmosphere.
    [0297] In this example, a magnetic field was not used in order to compare the samples obtained with the magnets of example 1. The application of a magnetic field in step b) would provide an increase in anisotropy according to example 2 and is applicable to the different materials in this example 3.
    [0299] Table 6. Properties of permanent magnets obtained by the process of the present invention.
    [0301]
    [0302]
    [0305] * Regarding the theoretical density of SFO
    [0307] Figure 10A shows a micrograph by means of scanning electron microscopy of a magnet based on 90% by weight of SFO and 10% by weight of starting nSFO and processed using glacial acetic acid as organic solvent at 50% by weight with respect to the starting material which after compaction was subjected to heating under pressure at a temperature of 1900C for 2 h and a uniaxial pressure of 375 MPa (M20).
    [0309] Regarding the M13 magnet obtained under the same conditions using 100% SFO as starting powder, a lower degradation of the SFO crystalline phase was identified. After a heat treatment at 11000C for 2 h (M21), a greater effectiveness in controlling grain growth was observed, which is limited to an average value of ~ 2 pm as shown in Figure 10B. During the thermal treatment at 11000C for 2 h there is an increase in the densification of the compact until it reaches 92% relative density with respect to the theoretical density. An advantage of incorporating nanoparticles into the initial mixture is the refinement of the grain sizes showing a single mode. In this way, the larger particles in the starting powder are refined during the processing of the present invention to generate a monomodal microstructure, that is, with a homogeneous size distribution.
    [0311] In the case of using oleic acid together with the starting powder after the compaction process at a temperature of 270 ° C for 3 h under a uniaxial pressure of 670 MPa (M22), it results in a lower relative density after the low heating process. pressure and the crystalline phase of SFO is maintained without degradation. After heat treatment at 1100 ° C for 2 h (M23), 92% relative density was reached with respect to the theoretical density, as in the case of using glacial acetic acid (M21).
    [0313] An analysis by X-ray diffraction from a Rietveld refinement determined a partial decomposition of SFO for the M20 magnet when using glacial acetic acid with a percentage of crystalline phases of 96% SFO and 4% iron oxide a-Fe203 , whereas when using oleic acid as organic solvent, no decomposition of the SFO phase (M22, 100% SFO). After the heat treatment process at 11000C for 2 h, regardless of the organic solvent used in the process, 100% SFO was identified for M21 and M23. The magnetic signal after the presented process is associated with a magnetic hysteresis cycle characteristic of a hard material such as SFO, figure 11.
    [0315] Therefore, the incorporation of SFO nanoparticles in the mixture with SFO improves the crystalline stability of the compacts after heating under pressure which translates into a greater control of the grain size of the magnets once they have been heat treated. This greater homogeneity in the grain size of the sintered ceramic magnet of the present invention has a monomodal microstructure that results in an advantage related to the functional response of the material.
    [0317] Example 4. Obtaining a permanent magnet from mixtures of SFO microparticles and a soft magnetic phase (FMB) by the process of the invention
    [0319] A mixture of 95-90% by weight of strontium hexaferrite microparticles, SFO and 5-10% by weight of a soft magnetic phase, FMB selected from among
    [0320] • microparticles of Fe, mFe, of 12 pm of average size;
    [0321] • NFe3Ü 4 iron oxide spinel nanoparticles of average size 60 nm
    [0322] • and Fe nanoparticles, nFe, of average size 80 nm comprising a surface layer of Fe 304 as passivation against spontaneous oxidation in an air atmosphere that is <15% by weight of the total particle.
    [0324] The mixture was homogenized by means of a dry milling process in an air atmosphere for 10 min in a Mixermill 8000 equipment using a nylon container and yttria stabilized zirconia balls of 1 mm in diameter.
    [0326] From said mixture, the procedure described in example 1 was followed, which comprised: a) homogeneous mixing of the mixture of SFO and mFe, nFe3Ü 4 or previous nFe with an organic solvent of glacial acetic acid;
    [0327] b) compacting the homogeneous mixture obtained in step (a) at a uniaxial pressure of 200 MPa for a period of 5 min;
    [0328] c) heating the product obtained in step b) under uniaxial pressure between 20 MPa and 5000 MPa at a temperature between 1200C and 3000C, and for a period of time between 30 min and 4h;
    [0329] d) cooling the product obtained in step (c) until reaching a temperature between 80 and 120 ° C to facilitate the extraction of the compacts, and subsequent cooling to room temperature between 18 ° C and 400 ° C;
    [0330] and e) sintering the product obtained in step (d) at a temperature between 10,000 ° C and 1150 ° C in the presence of an air atmosphere.
    [0332] In this example, a magnetic field was not used in order to compare the samples obtained with the magnets of example 1. The application of a magnetic field in step b) would provide an increase in anisotropy according to example 2 and is applicable to the different materials in this example 4.
    [0334] The percentage by weight of SFO and FMB, as well as the conditions during sintering are indicated in table 7, where the main parameters of the process of the invention followed to obtain magnets M24 to M29 are summarized.
    [0336] Table 7. Properties of permanent magnets obtained by the process of the present invention.
    [0338]
    [0339]
    [0342] * Regarding the theoretical density of SFO
    [0344] Figures 12A, 12C and 12E show micrographs by means of scanning electron microscopy of the magnets based on SFO incorporating 10% mFe (M24), 5% nFe (M26) and 10% nFe 3 Ü 4 (M28) respectively, and compacted using acid. glacial acetic as an organic solvent at 50% by weight of the magnetic material (SFO + FMB) and heated under uniaxial pressure of 375 MPa at a heating temperature of 1900C for 2 h. In all cases, a bimodal particle size was distinguished, consisting of microparticles with a size of 1-2 pm and nanostructures with particles of size <100 nm. During the heating process under pressure, an improvement in the apparent density is obtained, reaching densities greater than 75% with respect to the theoretical density of SFO.
    [0346] After the thermal treatment of the compounds at 1100 ° C for 2 h, the magnets M25 (Figure 12B), M27 (Figure 12D) and M29 (Figure 12F), obtained from the mixture of SFO 10% mFe, 5% nFe and 10% nFe 3 Ü 4 respectively, an increase in particle size was observed, reaching an average of 2 pm with a more homogeneous particle distribution and a relative density compared to the theoretical density of the resulting magnets greater than 91%; said bulk density is advantageous for the functionality of the magnet.
    [0348] Magnets M24, M26 and M28 (samples obtained from a sintering process without heat treatment) exhibited partial decomposition of the starting SFO. In the case of sample M24, the decomposition was almost complete. After the heat treatment process at 1100 ° C for 2h, magnets M25, M27 and M29 presented a partial recrystallization of SFO, identifying a percentage of secondary phase corresponding to iron oxide a-Fe 203 less than 24%, figure 13.
    [0350] The magnetic response of the composite magnets M24 to M29 is presented in figure 14. Parts M24, M26 and M28 exhibited magnetic hysteresis cycles that can be explained by the composition of the phases that comprise them, due to the phase transformation induced during the process. For example, the M24 magnet presented a cycle associated with a soft magnetic phase that is explained by the 97% crystalline phase as Fe 3 Ü 4 identified after sintering. Specifically for M24 and M26 magnets, their low density did not provide sufficient mechanical integrity.
    [0352] After sintering heat treatment at 11000C for 2 h, recrystallization of SFO results in an improvement in magnetic properties. The M25, M27 and M29 magnets had a coercive field greater than 2.5 kOe, even 3.0 kOe for the M29 magnet. The ratio of remanence magnetization to saturation magnetization became 0.67, 0.73 and 0.72, and saturation magnetization to 45.6 emu / g, 58.7 emu / g and 55.0 emu / g for the M25, M27 and M29 respectively.
    [0354] The incorporation of soft magnetic phases in the starting mixture increases the decomposition of the SFO phase in step c) of the process of the present invention. However, after step e) the resulting properties of the magnets showed an improvement in densification following the process of the present invention and a microstructure characterized in that said grain sizes are lower than the average grain sizes of the sintered samples following the process of the present invention that only uses starting SFO (example 1). Despite the presence of secondary phases, the reduction in the average size of the grains of the densified materials in Example 4 corresponds to a higher magnetic response than that corresponding to the densified materials in Examples 1 and 2.
    权利要求:
    Claims (10)
    [1]
    1. A process for obtaining a permanent ceramic magnet comprising • hard magnetic particles in the form of platelets with a ferrite or hexaferrite composition of the formula MFe ^ Oig, where M is a divalent alkaline earth metal selected from Sr + 2, Ba +2 and any combination thereof, and where said magnetic particles have a bimodal particle size distribution with a first particle size between 100 nm and 500 nm and a second particle size between 1 pm and 5 pm,
    characterized by comprising the following stages:
    a) mix homogeneously
    • hard magnetic particles of ferrite or hexaferrite composition of formula MFei 2 Üi 9 , where M is a divalent alkaline earth metal selected from among Sr + 2, Ba +2 and any of their combinations, of particle size between
    101 nmy 10 pm,
    • and an organic solvent;
    where the percentage of the organic solvent ranges from 5% to 50% by weight with respect to the total weight of the mixture,
    b) compacting the homogeneous mixture obtained in step (a) at a uniaxial pressure of between 5 MPa and 360 MPa for a period of time between 6 s and 5 min;
    c) heating the product obtained in step b) under uniaxial pressure of 20 MPa and 5000 MPa at a temperature of between 1200C and 300 0 C, and for a period of time between 30 min y4h;
    d) cooling the product obtained in step (c) until reaching a temperature between 80 and 1200C to facilitate the extraction of the compacts, and subsequent cooling to room temperature between 18 ° C and 0 ° C;
    and e) sintering the product obtained in step (d) at a temperature between 10,000 ° C and 1150 ° C in the presence of an air atmosphere.
    [2]
    2. The process according to claim 1, wherein the mixture of step (a) further comprises
    • hard magnetic particles with a ferrite or hexaferrite composition of the formula MFei 2 Üi 9 , where M is a divalent alkaline earth metal selected from Sr + 2, Ba +2 and any of their combinations, with a particle size between 5 nm and 100 nm.
    [3]
    3. The process according to any of claims 1, wherein the mixture of step (a) further comprises
    • soft magnetic particles of Fe or Fe 3 Ü 4 selected from particles of particle size between 10 pm and 15 pm or particles of particle size between 5nm and 100nm.
    [4]
    4. The process according to any one of claims 1 to 3, wherein step (a) is carried out in the presence of an atmosphere of the same organic solvent used in the mixture.
    [5]
    5. The process according to any of claims 1 to 4, wherein the organic solvent of step (a) is an acidic organic solvent selected from glacial acetic acid (CH 3 COOH), oleic acid (C 18 H 34 O 2 ) , lactic acid (C 3 H 6 O 3 ), formic acid (CH 2 O 2 ), citric acid (CeHsO ), oxalic acid (C 2 H 2 O 4 ), uric acid (C 5 H 4 N 4 O) or malic acid (C 4 H 6 O 5 ); or a combination thereof.
    [6]
    6. The process according to any of claims 1 to 4, wherein the organic solvent of step (a) is a basic organic solvent selected from anisole (C 7 H 8 O), aniline (C 6 H 7 N), purine (C 5 H 4 N 4 ), triethylamine (C 6 H 15 N) or oleamine (C 18 H 37 N); or a combination thereof.
    [7]
    The process according to any one of claims 1 to 6, wherein step (b) is carried out in a period of time between 6 s and 5 min.
    [8]
    8. The process according to any of claims 1 to 7, wherein step (b) is carried out in the presence of a magnetic field between 0.2T and 5 T.
    [9]
    9. The process according to any of claims 1 to 8, wherein the maximum temperature reached in step (e) of sintering is kept constant for a period of time between 30 min and 4h.
    [10]
    10. The process according to any of claims 1 to 9, wherein step (e) of Sintering is carried out by means of a thermal cycle with a heating rate of between 0.5 ° C / min and 10 ° C / min.
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    同族专利:
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN1937121A|2006-09-21|2007-03-28|上海大学|Method for preparing complex-phase nano crystal permanent-magnet ferrite material|
    WO2017137640A1|2016-02-08|2017-08-17|Universidad Complutense De Madrid|Permanently magnetic micro-composite material without rare earth elements and production method thereof|
    WO2019009320A1|2017-07-05|2019-01-10|株式会社村田製作所|Method for manufacturing sintered body, structure, and composite structure|
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