WO2024088426A1 - 一种硼硅包覆的金属软磁磁粉芯及其制备方法 - Google Patents

一种硼硅包覆的金属软磁磁粉芯及其制备方法 Download PDF

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WO2024088426A1
WO2024088426A1 PCT/CN2023/127840 CN2023127840W WO2024088426A1 WO 2024088426 A1 WO2024088426 A1 WO 2024088426A1 CN 2023127840 W CN2023127840 W CN 2023127840W WO 2024088426 A1 WO2024088426 A1 WO 2024088426A1
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magnetic powder
soft magnetic
preparation
borosilicate
coated
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PCT/CN2023/127840
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English (en)
French (fr)
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蔡岭文
张宁
羊建平
董江群
包大新
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横店集团东磁股份有限公司
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Publication of WO2024088426A1 publication Critical patent/WO2024088426A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/20—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder
    • H01F1/22—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
    • H01F1/24—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together the particles being insulated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets

Definitions

  • the embodiments of the present application relate to the technical field of metal soft magnetic materials, for example, a borosilicate-coated metal soft magnetic powder core and a preparation method thereof.
  • Soft magnetic material is an important magnetic functional material with good electromagnetic conversion properties.
  • the electronic components prepared are widely used in the fields of communications, power equipment, information technology, automatic control, etc.
  • Metal soft magnetic materials have the advantages of high saturation magnetization and good frequency characteristics.
  • the metal soft magnetic powder core prepared by molding, annealing, impregnation and curing can be used in high-frequency, high-efficiency, high-current, and miniaturized electronic components.
  • the surface coating of metal magnetic powder can increase the surface resistance of the powder core and reduce the eddy current loss under high-frequency use.
  • the current technology mainly covers the surface of magnetic powder particles with silicon-containing compounds, and the methods include inorganic coating, organic coating, inorganic-organic coating, etc.
  • CN110246679A discloses a method for preparing a metal soft magnetic powder core based on an organic/inorganic composite insulation process, and its technical scheme is: firstly, epoxy resin is used to perform organic insulation coating on metal magnetic powder, and then a silane coupling agent is used to modify and couple the nano silicon oxide powder generated by hydrolysis of epoxy resin and ethyl orthosilicate, so as to achieve composite insulation of epoxy resin and silicon oxide on metal magnetic powder, and then the insulated powder is cold pressed and formed, and the green body is annealed at high temperature to obtain a metal soft magnetic powder core with excellent DC bias performance and low high-frequency loss.
  • this process does not improve the insulation between particles well, and the magnetic loss of the obtained metal soft magnetic powder core is relatively high.
  • CN101599334A discloses a method for manufacturing a FeSiAl material with high resistivity and high magnetic permeability.
  • 1-10wt% Ni powder is added to FeSiAl magnetic powder, and a SiO2 layer is coated on the surface of the magnetic powder, which can significantly reduce its electrical conductivity without substantially changing the original magnetic properties, thereby greatly reducing losses.
  • the thickness of the SiO2 coating layer can be adjusted according to the concentration of added ethyl orthosilicate.
  • the method performs surface treatment on the coated powder, improves the dispersibility of the product, improves its processing performance, and significantly improves the physical and chemical properties of the product.
  • this method is difficult and the process is not easy to control.
  • CN103247403A discloses a method for preparing a metal soft magnetic powder core, which includes six steps: raw material screening, insulation coating, preparation of magnetic powder to be formed, pressing, heat treatment and surface spraying.
  • the method is simple and the equipment used is simple; the nano-oxide dispersion is used to insulate the magnetic powder, which has good effect, no pollution to the environment, and low raw material cost; the preparation process does not use organic solvents and organic binders, does not perform infiltration and curing treatment, and has low cost and no pollution; the metal soft magnetic powder core produced by this method has good magnetic performance stability, high quality factor and low core loss.
  • the coating effect of this preparation method is poor.
  • the embodiment of the present application provides a borosilicate-coated metal soft magnetic powder core and a preparation method thereof, wherein a chemically organically synthesized borosilicate-containing coating is uniformly coated on the surface of the soft magnetic powder.
  • the preparation process is easy to control, the insulation coating effect is good, and it has a prospect for large-scale industrial promotion and application.
  • an embodiment of the present application provides a method for preparing a borosilicate-coated metal soft magnetic powder core, the preparation method comprising the following steps:
  • the preparation method of the borosilicate coated metal soft magnetic powder core described in the present application uses raw materials siloxane, boric acid powder, a first solvent, a catalyst and water to perform hydrolysis reaction and polycondensation reaction in sequence to obtain a borosilicate-containing coating agent, which can form a glass network structure on the surface of soft magnetic powder particles, effectively improve the insulation coating on the surface of the soft magnetic powder, and then greatly increase the resistance of the metal soft magnetic powder core, and reduce eddy current loss under high-frequency use.
  • the preparation process of the preparation method described in the present application is easy to control, and the insulation coating effect is good.
  • the step of mixing siloxane, boric acid powder, a first solvent, a catalyst and water in step (1) comprises: first mixing siloxane and boric acid powder to obtain a mixed solution, then adding the first solvent and the catalyst, stirring and heating to 50-100° C., and then adding water, wherein the stirring and heating to 50-100° C. may be, for example, 50°C, 60°C, 70°C, 80°C, 90°C or 100°C, etc., but are not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the siloxane in step (1) comprises polydimethylsiloxane and/or dimethyldiethoxysilane.
  • the purity of the boric acid powder is above 99.9%, for example, it can be 99.9%, 99.91%, 99.92%, 99.94%, 99.95% or 99.98%, etc., but it is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the particle size of the boric acid powder is 5 to 50 ⁇ m, for example, 5 ⁇ m, 10 ⁇ m, 20 ⁇ m, 30 ⁇ m, 40 ⁇ m or 50 ⁇ m, etc., but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the mass ratio of the siloxane to the boric acid powder is 10:(0.5-3), for example, it can be 10:0.5, 10:0.8, 10:1, 10:1.5, 10:2 or 10:3, etc., but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the present application preferably uses a mass ratio of 10:(0.5-3) for siloxane and boric acid powder, which is conducive to forming a borosilicate coating with a glass mesh structure on the surface of the soft magnetic powder particles, thereby increasing the surface resistance of the metal soft magnetic powder core and reducing the eddy current loss under high-frequency use.
  • the mass ratio of siloxane and boric acid powder is lower than 10:0.5, the silicon content of the powder coating is low and the effect of reducing eddy current loss is poor; when the mass ratio of siloxane and boric acid powder is higher than 10:3, the silicon content of the powder coating is too high, which greatly reduces the magnetic permeability of the borosilicate-coated metal soft magnetic powder core.
  • the first solvent comprises any one of methanol, ethanol, isopropanol or n-butanol, or a combination of at least two of them, wherein typical but non-limiting combinations include a combination of methanol and ethanol, a combination of isopropanol and n-butanol, a combination of ethanol and isopropanol, or a combination of n-butanol, methanol and isopropanol.
  • the catalyst comprises any one of hydrochloric acid, sulfuric acid or nitric acid or a combination of at least two thereof, wherein typical but non-limiting combinations include a combination of hydrochloric acid and sulfuric acid, a combination of nitric acid and hydrochloric acid or a combination of sulfuric acid, nitric acid and hydrochloric acid.
  • the mass concentration of the catalyst is 2 to 10 mol/mL, for example, 2 mol/mL, 3 mol/mL, 5 mol/mL, 7 mol/mL, 8 mol/mL or 10 mol/mL, etc., but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the volume ratio of the first solvent to the catalyst is 10:(0.1-0.5), for example, 10:0.1, 10:0.2, 10:0.3, 10:0.4 or 10:0.5, etc., but are not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the water comprises deionized water.
  • the amount of water added is 1-5% of the mass of the silicone and boric acid powder, for example, 1%, 2%, 3%, 4% or 5%, etc., but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the hydrolysis reaction time is 0.5 to 5 h, for example, 0.5 h, 1 h, 2 h, 3 h, 4 h or 5 h, etc., but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the polycondensation reaction in step (1) is carried out in a distillation apparatus.
  • the hydrolyzate is distilled under reduced pressure in the distillation apparatus.
  • the vacuum degree of the reduced pressure distillation is 0.02-0.15 MPa, for example, it can be 0.02 MPa, 0.05 MPa, 0.1 MPa, 0.12 MPa, 0.14 MPa or 0.15 MPa, but it is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the temperature of the polycondensation reaction is 80-150°C, for example, 80°C, 90°C, 100°C, 130°C, 140°C or 150°C, etc., but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the polycondensation reaction time is 1 to 20 h, for example, 1 h, 3 h, 5 h, 10 h, 15 h or 20 h, etc., but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the mass ratio of the borosilicate-containing coating agent, the soft magnetic powder and the second solvent in step (2) is (0.01-0.5):10:(0.5-1.5), for example, it can be 0.01:10:0.5, 0.05:10:0.8, 0.1:10:0.9, 0.2:10:1, 0.3:10:1.2 or 0.5:10:1.5, etc., but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the soft magnetic powder comprises any one of iron-nickel magnetic powder, iron-silicon magnetic powder, iron-silicon-aluminum magnetic powder, iron-nickel-molybdenum magnetic powder, amorphous magnetic powder or nanocrystalline magnetic powder, or a combination of at least two of them, wherein typical but non-limiting combinations include a combination of iron-nickel magnetic powder and iron-silicon magnetic powder, a combination of iron-silicon-aluminum magnetic powder and iron-nickel-molybdenum magnetic powder, a combination of iron-nickel magnetic powder and iron-silicon-aluminum magnetic powder, or a combination of iron-nickel-molybdenum magnetic powder, iron-nickel magnetic powder and iron-silicon magnetic powder.
  • the second solvent comprises acetone.
  • the coated soft magnetic powder is also sequentially dried and sieved.
  • the step (3) of mixing the coated soft magnetic powder, binder and release agent comprises: first mixing the coated soft magnetic powder and binder, drying them, and then adding the release agent.
  • the mass ratio of the coated soft magnetic powder, binder and release agent is 10:(0.01-0.1):(0.01-0.1), for example, it can be 10:0.01:0.01, 10:0.02:0.03, 10:0.05:0.05, 10:0.06:0.07, 10:0.08:0.09 or 10:0.1:0.1, etc., but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the adhesive comprises any one of silicone resin, epoxy resin or phenolic resin or a combination of at least two of them, wherein typical but non-limiting combinations include a combination of silicone resin and epoxy resin, a combination of phenolic resin and silicone resin, or a combination of epoxy resin, phenolic resin and silicone resin.
  • the release agent comprises any one of zinc stearate, aluminum stearate or graphite or a combination of at least two thereof, wherein typical but non-limiting combinations include a combination of zinc stearate and aluminum stearate, a combination of graphite and zinc stearate, or a combination of aluminum stearate, graphite and zinc stearate.
  • the pressing pressure in step (3) is 1000-3000 MPa, for example, it can be 1000 MPa, 1050 MPa, 2000 MPa, 2500 MPa or 3000 MPa, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the present application preferably uses a pressing pressure of 1000-3000 MPa, which has the advantages of increasing the density of the borosilicate-coated metal soft magnetic powder core and ensuring that the insulating layer is not damaged.
  • the annealing process is performed in a nitrogen atmosphere.
  • the annealing temperature is 500-800°C, for example, 500°C, 550°C, 600°C, 700°C, 770°C or 800°C, but is not limited to the listed values, and other unlisted values within the range are also applicable.
  • the present application preferably uses an annealing treatment temperature of 500-800° C., which has the advantages of removing stress and reducing hysteresis loss.
  • the annealing treatment time is 0.1 to 8 hours, for example, it can be 0.1 h, 0.5 h, 1 h, 2 h, 5 h or 8 h, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the preparation method comprises the following steps:
  • the siloxane includes polydimethylsiloxane and/or dimethyldiethoxysilane; the purity of the boric acid powder is above 99.9%; the particle size of the boric acid powder is 5 to 50 ⁇ m; the first solvent includes any one of methanol, ethanol, isopropanol or n-butanol or a combination of at least two; the catalyst includes any one of hydrochloric acid, sulfuric acid or nitric acid or a combination of at least two; the mass concentration of the catalyst is 2 to 10 mol/mL; the water includes deionized water; the amount of water added is 1 to 5 wt% of the mass of the siloxane and the boric acid powder; the vacuum degree of the reduced pressure distillation is 0.02 to 0.15 MPa;
  • the soft magnetic powder comprises any one of iron-nickel magnetic powder, iron-silicon magnetic powder, iron-silicon-aluminum magnetic powder, iron-nickel-molybdenum magnetic powder, amorphous magnetic powder or nanocrystalline magnetic powder, or a combination of at least two thereof; the second solvent comprises acetone; the coated soft magnetic powder is further dried and sieved in sequence;
  • the mass ratio of the coated soft magnetic powder, binder and release agent is 10:(0.01-0.1):(0.01-0.1);
  • the binder includes any one of silicone resin, epoxy resin or phenolic resin or a combination of at least two of them;
  • the release agent includes any one of zinc stearate, aluminum stearate or graphite or a combination of at least two of them.
  • an embodiment of the present application further provides a borosilicate coated metal soft magnetic powder core, wherein the metal soft magnetic powder core is prepared by the preparation method of the borosilicate coated metal soft magnetic powder core described in the first aspect.
  • the method for preparing the borosilicate-coated metal soft magnetic powder core uses raw boric acid powder to chemically and organically synthesize the borosilicate coating, which effectively improves the insulating coating on the surface of the metal soft magnetic powder core and increases the resistance of the powder core;
  • the borosilicate coated metal soft magnetic powder core provided in the embodiments of the present application has excellent magnetic properties, high magnetic permeability and low magnetic loss, and has a prospect for large-scale industrial promotion and application.
  • This embodiment provides a method for preparing a borosilicate-coated metal soft magnetic powder core, the preparation method comprising the following steps:
  • the purity of the boric acid powder is 99.9%; the particle size of the boric acid powder is 30 ⁇ m; the mass concentration of the catalyst is 5 mol/mL; the amount of water added is 2 wt% of the mass of the siloxane and the boric acid powder; the vacuum degree of the reduced pressure distillation is 0.02 MPa;
  • the coated soft magnetic powder and the binder silicone resin are first mixed, dried, and then the release agent zinc stearate is added, followed by pressing at a pressure of 1500 MPa and annealing at a temperature of 600° C. for 5 h in a nitrogen atmosphere to obtain a borosilicate-coated metal soft magnetic powder core; the mass ratio of the coated soft magnetic powder, the binder and the release agent is 10:0.05:0.05.
  • This embodiment provides a method for preparing a borosilicate-coated metal soft magnetic powder core, the preparation method comprising the following steps:
  • the purity of the boric acid powder is 99.93%; the particle size of the boric acid powder is 10 ⁇ m; the mass concentration of the catalyst is 2 to 10 mol/mL; the amount of water added is 1 to 5 wt% of the mass of the siloxane and the boric acid powder;
  • the vacuum degree of the reduced pressure distillation is 0.05MPa;
  • the coated soft magnetic powder and the binder epoxy resin are first mixed, dried, and then the release agent aluminum stearate is added, followed by pressing at a pressure of 1500 MPa and annealing at a temperature of 650° C. for 2 h in a nitrogen atmosphere to obtain a borosilicate coated metal soft magnetic powder core; the mass ratio of the coated soft magnetic powder, the binder and the release agent is 10:0.01:0.05.
  • This embodiment provides a method for preparing a borosilicate-coated metal soft magnetic powder core, the preparation method comprising the following steps:
  • the purity of the boric acid powder is 99.95%; the particle size of the boric acid powder is 25 ⁇ m; the mass concentration of the catalyst is 4 mol/mL; the amount of water added is 4 wt% of the mass of the siloxane and the boric acid powder; the vacuum degree of the reduced pressure distillation is 0.05 MPa;
  • the coated soft magnetic powder and the binder phenolic resin are first mixed, dried, and then the release agent graphite is added, and then pressed at a pressure of 1500 MPa and annealed at a temperature of 700° C. for 7 h in a nitrogen atmosphere to obtain a borosilicate coated metal soft magnetic powder core; the mass ratio of the coated soft magnetic powder, the binder and the release agent is 10:0.09:0.03.
  • This embodiment provides a method for preparing a borosilicate-coated metal soft magnetic powder core, the preparation method comprising the following steps:
  • (1) firstly mix polydimethylsiloxane and boric acid powder in a mass ratio of 10:0.5 to obtain a mixed solution, then add the first solvent ethanol and the catalyst sulfuric acid in a volume ratio of 10:0.5, stir and heat to 50°C, Deionized water was added to carry out a hydrolysis reaction for 5 hours; the hydrolysis product was subjected to reduced pressure distillation in a distillation device, and a polycondensation reaction was carried out at a temperature of 120° C. for 6 hours to obtain a borosilicate-containing coating agent;
  • the purity of the boric acid powder is above 99.9%; the particle size of the boric acid powder is 50 ⁇ m; the mass concentration of the catalyst is 10 mol/mL; the amount of water added is 2.4 wt% of the mass of the siloxane and the boric acid powder; the vacuum degree of the reduced pressure distillation is 0.1 MPa;
  • the coated soft magnetic powder and the binder epoxy resin are first mixed, dried, and then the release agent zinc stearate is added, followed by pressing at a pressure of 1500 MPa and annealing at a temperature of 700° C. in a nitrogen atmosphere for 5.5 h to obtain a borosilicate-coated metal soft magnetic powder core; the mass ratio of the coated soft magnetic powder, the binder and the release agent is 10:0.08:0.01.
  • This embodiment provides a method for preparing a borosilicate-coated metal soft magnetic powder core, the preparation method comprising the following steps:
  • the purity of the boric acid powder is 99.92%; the particle size of the boric acid powder is 5 ⁇ m; the mass concentration of the catalyst is 2 mol/mL; the amount of water added is 1 wt% of the mass of the siloxane and the boric acid powder; the vacuum degree of the reduced pressure distillation is 0.02 MPa;
  • the coated soft magnetic powder and the binder silicone resin are first mixed, dried, and then the release agent aluminum stearate is added, followed by pressing at a pressure of 1000 MPa and annealing at a temperature of 500° C. for 8 h in a nitrogen atmosphere to obtain a borosilicate coated metal soft magnetic powder core; the mass ratio of the coated soft magnetic powder, the binder and the release agent is 10:0.01:0.1.
  • This embodiment provides a method for preparing a borosilicate-coated metal soft magnetic powder core, the preparation method comprising the following steps:
  • the purity of the boric acid powder is 99.98%; the particle size of the boric acid powder is 50 ⁇ m; the mass concentration of the catalyst is 10 mol/mL; the amount of water added is 5 wt% of the mass of the siloxane and the boric acid powder; the vacuum degree of the reduced pressure distillation is 0.15 MPa;
  • the coated soft magnetic powder and the binder silicone resin are first mixed, dried, and then the release agent zinc stearate is added, followed by pressing at a pressure of 3000 MPa and annealing at a temperature of 800° C. in a nitrogen atmosphere for 0.1 h to obtain a borosilicate-coated metal soft magnetic powder core; the mass ratio of the coated soft magnetic powder, the binder and the release agent is 10:0.1:0.5.
  • the present embodiment provides a method for preparing a borosilicate-coated metal soft magnetic powder core.
  • the preparation method is the same as that of Embodiment 1 except that the mass ratio of siloxane to boric acid powder in step (1) is replaced from 10:0.5 to 10:0.1.
  • the present embodiment provides a method for preparing a borosilicate-coated metal soft magnetic powder core.
  • the preparation method is the same as that of Embodiment 1 except that the mass ratio of siloxane to boric acid powder in step (1) is replaced from 10:0.5 to 10:4.
  • This embodiment provides a method for preparing a borosilicate-coated metal soft magnetic powder core.
  • the preparation method is the same as that of Embodiment 1, except that the pressing pressure in step (3) is replaced by 500 MPa instead of 1500 MPa.
  • This embodiment provides a method for preparing a boron silicon-coated metal soft magnetic powder core.
  • the preparation method Except that the pressing pressure in step (3) is replaced by 3500 MPa instead of 1500 MPa, the rest is the same as Example 1.
  • This embodiment provides a method for preparing a borosilicate-coated metal soft magnetic powder core.
  • the preparation method is the same as that of Embodiment 1 except that the annealing temperature in step (3) is replaced by 400°C instead of 600°C.
  • This embodiment provides a method for preparing a borosilicate-coated metal soft magnetic powder core.
  • the preparation method is the same as that of Embodiment 1 except that the annealing temperature in step (3) is replaced from 600°C to 900°C.
  • This comparative example provides a method for preparing a borosilicate-coated metal soft magnetic powder core, the preparation method comprising the following steps:
  • 500 mesh iron-nickel magnetic powder was passivated in phosphoric acid, 0.5wt% kaolin was added for insulation coating, and 0.3wt% silicone resin was added for secondary coating.
  • Phenolic resin was added to the coated magnetic powder as a binder, zinc stearate was used as a release agent, and the powder was molded at 1500MPa and annealed in a nitrogen atmosphere at 600°C to obtain a ring sample.
  • This comparative example provides a method for preparing a borosilicate-coated metal soft magnetic powder core.
  • the preparation method is the same as Example 1 except that boric acid powder is not added in step (1).
  • This comparative example provides a method for preparing a borosilicate-coated metal soft magnetic powder core.
  • the preparation method is the same as that of comparative example 1 except that iron-nickel is replaced by iron-silicon magnetic powder.
  • This comparative example provides a method for preparing a borosilicate-coated metal soft magnetic powder core.
  • the preparation method is the same as that of comparative example 1 except that iron-nickel is replaced by sendustine magnetic powder.
  • Example 2 Combining Example 1 with Examples 7 to 8, it can be seen that the mass ratio of siloxane to boric acid powder in step (1) of Example 7 is 10:0.1, and the magnetic permeability of the obtained borosilicate-coated metal soft magnetic powder core is significantly lower than that of Example 1; however, under the conditions of 50kHz, 100mT and under the conditions of 100kHz, 100mT, The loss is equivalent to that in Example 1; in step (1) of Example 8, the mass ratio of siloxane to boric acid powder is 10:4, and the magnetic permeability of the obtained borosilicate-coated metal soft magnetic powder core is 132, the magnetic permeability is slightly improved, but the loss is significantly increased;
  • Example 1 Combining Example 1 with Examples 9 and 10, it can be seen that the pressure of the pressing molding in step (3) of Example 9 is relatively low, and the magnetic permeability of the obtained borosilicate coated metal soft magnetic powder core is relatively low, which is 76; the pressure of the pressing molding in step (3) of Example 10 is relatively high, and the magnetic permeability of the obtained borosilicate coated metal soft magnetic powder core is higher than that of Example 1, which is 141; however, the losses of the borosilicate coated metal soft magnetic powder cores obtained in Examples 9 and 10 are much higher than that in Example 1;
  • Example 1 Combining Example 1 with Examples 11 and 12, it can be seen that the annealing temperature in step (3) of Example 11 is relatively low, and the magnetic permeability of the obtained borosilicate-coated metal soft magnetic powder core is slightly lower than that of Example 1, but the loss is much higher than that of Example 1; the annealing temperature in step (3) of Example 12 is relatively high, and the magnetic permeability of the obtained borosilicate-coated metal soft magnetic powder core is equivalent to that of Example 1, but the loss is as high as 1210 mW/cm 3 under the conditions of 100 kHz and 100 mT;
  • Example 1 Combining Example 1 with Comparative Example 1, Example 3, Example 5 with Comparative Example 3, Example 4, Example 6 with Comparative Example 4, it can be seen that the preparation method of the borosilicate-coated metal soft magnetic powder core provided in the present application is applied to raw materials of iron-nickel, iron-silicon, and iron-silicon-aluminum magnetic powder. Compared with the methods of Comparative Examples 1, 3, and 4, the obtained borosilicate-coated metal soft magnetic powder core has high magnetic permeability and low loss;
  • the preparation method of the borosilicate coated metal soft magnetic powder core adopts a specific mass ratio of siloxane and boric acid powder, and uses the raw material boric acid powder to carry out chemical organic synthesis of the borosilicate coating under specific pressing pressure and specific annealing temperature conditions, which effectively improves the insulating coating on the surface of the metal soft magnetic powder core and increases the resistance of the powder core.
  • the obtained borosilicate coated metal soft magnetic powder core has excellent magnetic properties, high magnetic permeability and low magnetic loss.

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Abstract

一种硼硅包覆的金属软磁磁粉芯及其制备方法，所述制备方法包括如下步骤：(1)混合硅氧烷、硼酸粉、第一溶剂、催化剂和水，进行水解反应，水解产物经缩聚反应，得到含硼硅的包覆剂；(2)混合所述含硼硅的包覆剂、软磁粉末和第二溶剂，得到包覆后的软磁粉末；(3)混合所述包覆后的软磁粉末、粘结剂和脱模剂，依次经压制成型和退火处理，得到硼硅包覆的金属软磁磁粉芯。本申请所述制备方法采用化学有机合成含硼硅包覆物均匀包覆于软磁粉末表面，有效改善软磁粉末表面的绝缘包覆，进而大幅度提高金属软磁磁粉芯的电阻，降低高频使用下的涡流损耗，具有大规模工业化推广应用前景。

Description

一种硼硅包覆的金属软磁磁粉芯及其制备方法 技术领域
本申请实施例涉及金属软磁材料技术领域，例如一种硼硅包覆的金属软磁磁粉芯及其制备方法。
背景技术
软磁材料是一种重要的磁性功能材料，具有良好的电磁转换功能特性，制备的电子元器件广泛用于通讯、电力设备、信息技术、自动控制等领域。金属软磁材料具有高饱和磁化强度、良好的频率特性等优点，其与绝缘粘结剂包覆混合后，通过成型、退火处理、含浸固化等过程制备而成的金属软磁粉芯，可用于高频、高能效、大电流、小型化的电子元器件使用场景。
金属磁粉的表面包覆可提高粉芯的表面电阻，降低高频使用下的涡流损耗。目前的技术主要以在磁粉颗粒表面包覆含硅的化合物为主，手段有无机包覆、有机包覆、无机-有机包覆等。
CN110246679A公开了一种基于有机/无机复合绝缘工艺的金属软磁粉芯制备方法，其技术方案为：首先采用环氧树脂对金属磁粉进行有机绝缘包覆，然后利用硅烷偶联剂对环氧树脂和正硅酸乙酯水解生成的纳米氧化硅粉末进行改性偶联，实现环氧树脂与氧化硅对金属磁粉的复合绝缘，在此基础上对绝缘后粉末进行冷压成型，并将生坯进行高温退火，得到直流偏置性能优异、高频损耗低的金属软磁粉芯。但该工艺并未较好地改善颗粒间的绝缘性，得到的金属软磁粉芯的磁损耗较高。
CN101599334A公开了一种高电阻率高磁导率的铁硅铝材料的制造方法，在FeSiAl磁粉中加入1～10wt％Ni粉，并在磁粉的表面包覆SiO2层，可以在基本不改变原有磁性能基础上大幅度降低了其导电性能，大大减少了损耗。而且SiO2包覆层的厚度可以根据加入的正硅酸乙酯浓度来调节。所述方法对包覆粉进行表面处理，改善产品的分散性，提高其加工性能，并显著提高产品理化性能。但该方法难度较高且过程不易控制。
CN103247403A公开了一种金属软磁粉芯的制备方法，该方法包括原料过筛、绝缘包覆、制待成型磁粉、压制成型、热处理和表面喷涂六部分。制作工艺简 单，使用设备简单；选用这种纳米氧化物分散液对磁粉进行绝缘包覆，使用效果好，不污染环境，原料成本低；制备过程不使用有机溶剂与有机粘结剂，不做浸润固化处理，成本低且无污染；采用本方法制作的金属软磁粉芯具有良好的磁性能稳定性，较高的品质因数和较低的磁芯损耗。但该制备方法的包覆效果较差。
因此，开发一种绝缘包覆效果良好，能够提高磁粉芯的表面电阻，降低高频使用下的涡流损耗的硼硅包覆的金属软磁磁粉芯及其制备方法具有重要意义。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请实施例提供一种硼硅包覆的金属软磁磁粉芯及其制备方法，采用化学有机合成含硼硅包覆物均匀包覆于软磁粉末表面，制备过程易于控制，绝缘包覆效果良好，具有大规模工业化推广应用前景。
第一方面，本申请实施例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法包括如下步骤：
(1)混合硅氧烷、硼酸粉、第一溶剂、催化剂和水，进行水解反应，水解产物经缩聚反应，得到含硼硅的包覆剂；
(2)混合所述含硼硅的包覆剂、软磁粉末和第二溶剂，得到包覆后的软磁粉末；
(3)混合所述包覆后的软磁粉末、粘结剂和脱模剂，依次经压制成型和退火处理，得到硼硅包覆的金属软磁磁粉芯。
本申请所述的硼硅包覆的金属软磁磁粉芯的制备方法采用原料硅氧烷、硼酸粉、第一溶剂、催化剂和水依次进行水解反应和缩聚反应，得到含硼硅的包覆剂，可以在软磁粉末颗粒表面形成玻璃网状结构，有效改善软磁粉末表面的绝缘包覆，进而大幅度提高金属软磁磁粉芯的电阻，降低高频使用下的涡流损耗。本申请所述制备方法的制备过程易于控制，绝缘包覆效果良好。
优选地，步骤(1)所述混合硅氧烷、硼酸粉、第一溶剂、催化剂和水的步骤包括：先混合硅氧烷和硼酸粉，得到混合溶液，之后加入第一溶剂和催化剂，搅拌并升温至50～100℃后，加入水，其中搅拌并升温至50～100℃，例如可以是 50℃、60℃、70℃、80℃、90℃或100℃等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，步骤(1)所述硅氧烷包括聚二甲基硅氧烷和/或二甲基二乙氧基硅烷。
优选地，所述硼酸粉的纯度为99.9％以上，例如可以是99.9％、99.91％、99.92％、99.94％、99.95％或99.98％等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，所述硼酸粉的粒径为5～50μm，例如可以是5μm、10μm、20μm、30μm、40μm或50μm等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，所述硅氧烷和硼酸粉的质量比为10:(0.5～3)，例如可以是10:0.5、10:0.8、10:1、10:1.5、10:2或10:3等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
本申请优选所述硅氧烷和硼酸粉的质量比为10:(0.5～3)，有利于在软磁粉末颗粒表面形成具有玻璃网状结构的含硼硅包覆物，进而提高金属软磁磁粉芯的表面电阻，降低高频使用下的涡流损耗。当硅氧烷和硼酸粉的质量比低于10:0.5，会导致粉末包覆物硅含量低，降涡流损耗效果差；当硅氧烷和硼酸粉的质量比高于10:3，会导致粉末包覆物硅含量过高，大幅降低硼硅包覆的金属软磁磁粉芯的磁导率。
优选地，步骤(1)所述第一溶剂包括甲醇、乙醇、异丙醇或正丁醇中的任意一种或至少两种的组合，其中典型但非限制性的组合包括甲醇和乙醇的组合，异丙醇和正丁醇的组合，乙醇和异丙醇的组合或正丁醇、甲醇和异丙醇三者的组合。
优选地，所述催化剂包括盐酸、硫酸或硝酸中的任意一种或至少两种的组合，其中典型但非限制性的组合包括盐酸和硫酸的组合，硝酸和盐酸的组合或硫酸、硝酸和盐酸三者的组合。
优选地，所述催化剂的质量浓度为2～10mol/mL，例如可以是2mol/mL、3mol/mL、5mol/mL、7mol/mL、8mol/mL或10mol/mL等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，所述第一溶剂和催化剂的体积比为10:(0.1～0.5)，例如可以是10:0.1、 10:0.2、10:0.3、10:0.4或10:0.5等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，所述水包括去离子水。
优选地，所述水的添加量为硅氧烷和硼酸粉质量的1～5％，例如可以是1％、2％、3％、4％或5％等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，所述水解反应的时间为0.5～5h，例如可以是0.5h、1h、2h、3h、4h或5h等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，步骤(1)所述缩聚反应在蒸馏装置中进行。
优选地，在所述蒸馏装置中对水解产物进行减压蒸馏。
优选地，所述减压蒸馏的真空度为0.02～0.15MPa，例如可以是0.02MPa、0.05MPa、0.1MPa、0.12MPa、0.14MPa或0.15MPa等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，所述缩聚反应的温度为80～150℃，例如可以是80℃、90℃、100℃、130℃、140℃或150℃等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，所述缩聚反应的时间为1～20h，例如可以是1h、3h、5h、10h、15h或20h等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，步骤(2)所述含硼硅的包覆剂、软磁粉末和第二溶剂的质量比为(0.01～0.5):10:(0.5～1.5)，例如可以是0.01:10:0.5、0.05:10:0.8、0.1:10:0.9、0.2:10:1、0.3:10:1.2或0.5:10:1.5等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，所述软磁粉末包括铁镍磁粉、铁硅磁粉、铁硅铝磁粉、铁镍钼磁粉、非晶磁粉或纳米晶磁粉中的任意一种或至少两种的组合，其中典型但非限制性的组合包括铁镍磁粉和铁硅磁粉的组合，铁硅铝磁粉和铁镍钼磁粉的组合，铁镍磁粉和铁硅铝磁粉的组合或铁镍钼磁粉、铁镍磁粉和铁硅磁粉三者的组合。
优选地，所述第二溶剂包括丙酮。
优选地，所述包覆后的软磁粉末还依次进行干燥和筛分处理。
优选地，步骤(3)混合所述包覆后的软磁粉末、粘结剂和脱模剂的步骤包括：先混合所述包覆后的软磁粉末和粘结剂，烘干处理后，再加入脱模剂。
优选地，所述包覆后的软磁粉末、粘结剂和脱模剂的质量比为10:(0.01～0.1):(0.01～0.1)，例如可以是10:0.01:0.01、10:0.02:0.03、10:0.05:0.05、10:0.06:0.07、10:0.08:0.09或10:0.1:0.1等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，所述粘结剂包括硅树脂、环氧树脂或酚醛树脂中的任意一种或至少两种的组合，其中典型但非限制性的组合包括硅树脂和环氧树脂的组合，酚醛树脂和硅树脂的组合或环氧树脂、酚醛树脂和硅树脂三者的组合。
优选地，所述脱模剂包括硬脂酸锌、硬脂酸铝或石墨中的任意一种或至少两种的组合，其中典型但非限制性的组合包括硬脂酸锌和硬脂酸铝的组合，石墨和硬脂酸锌的组合或硬脂酸铝、石墨和硬脂酸锌三者的组合。
优选地，步骤(3)所述压制成型的压力为1000～3000MPa，例如可以是1000MPa、1050MPa、2000MPa、2500MPa或3000MPa等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
本申请优选所述压制成型的压力为1000～3000MPa，具有提高硼硅包覆的金属软磁磁粉芯密实度，且可保证绝缘层不被破坏的优点。
优选地，所述退火处理在氮气气氛中进行。
优选地，所述退火处理的温度为500～800℃，例如可以是500℃、550℃、600℃、700℃、770℃或800℃等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
本申请优选所述退火处理的温度为500～800℃，具有去除应力，降低磁滞损耗的优点。
优选地，所述退火处理的时间为0.1～8h，例如可以是0.1h、0.5h、1h、2h、5h或8h等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
作为本申请优选的技术方案，所述制备方法包括如下步骤：
(1)先按照质量比为10:(0.5～3)混合硅氧烷和硼酸粉，得到混合溶液，之后加入体积比为10:(0.1～0.5)的第一溶剂和催化剂，搅拌并升温至50～100℃后，加入水，进行水解反应0.5～5h；在蒸馏装置中对水解产物进行减压蒸馏，进行 温度为80～150℃的缩聚反应1～20h，得到含硼硅的包覆剂；
所述硅氧烷包括聚二甲基硅氧烷和/或二甲基二乙氧基硅烷；所述硼酸粉的纯度为99.9％以上；所述硼酸粉的粒径为5～50μm；所述第一溶剂包括甲醇、乙醇、异丙醇或正丁醇中的任意一种或至少两种的组合；所述催化剂包括盐酸、硫酸或硝酸中的任意一种或至少两种的组合；所述催化剂的质量浓度为2～10mol/mL；所述水包括去离子水；所述水的添加量为硅氧烷和硼酸粉质量的1～5wt％；所述减压蒸馏的真空度为0.02～0.15MPa；
(2)按照质量比为(0.01～0.5):10:(0.5～1.5)混合所述含硼硅的包覆剂、软磁粉末和第二溶剂，得到包覆后的软磁粉末；
所述软磁粉末包括铁镍磁粉、铁硅磁粉、铁硅铝磁粉、铁镍钼磁粉、非晶磁粉或纳米晶磁粉中的任意一种或至少两种的组合；所述第二溶剂包括丙酮；所述包覆后的软磁粉末还依次进行干燥和筛分处理；
(3)先混合所述包覆后的软磁粉末和粘结剂，烘干处理后，再加入脱模剂，依次经压力为1000～3000MPa的压制成型和氮气气氛中，温度为500～800℃的退火处理0.1～8h，得到硼硅包覆的金属软磁磁粉芯；
所述包覆后的软磁粉末、粘结剂和脱模剂的质量比为10:(0.01～0.1):(0.01～0.1)；所述粘结剂包括硅树脂、环氧树脂或酚醛树脂中的任意一种或至少两种的组合；所述脱模剂包括硬脂酸锌、硬脂酸铝或石墨中的任意一种或至少两种的组合。
第二方面，本申请实施例还提供一种硼硅包覆的金属软磁磁粉芯，所述金属软磁磁粉芯由第一方面所述的硼硅包覆的金属软磁磁粉芯的制备方法制得。
与相关技术相比，本申请实施例至少具有以下有益效果：
(1)本申请实施例提供的硼硅包覆的金属软磁磁粉芯的制备方法利用原料硼酸粉进行化学有机合成含硼硅包覆物，有效改善了金属软磁磁粉芯表面的绝缘包覆，提高了磁粉芯的电阻；
(2)本申请实施例提供的硼硅包覆的金属软磁磁粉芯的磁性能优越，磁导率高且磁损耗低具有大规模工业化推广应用前景。
在阅读并理解了详细描述后，可以明白其他方面。
具体实施方式
为便于理解本申请，本申请列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
下面对本申请进一步详细说明。但下述的实例仅仅是本申请的简易例子，并不代表或限制本申请的权利保护范围，本申请的保护范围以权利要求书为准。
实施例1
本实施例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法包括如下步骤：
(1)先按照质量比为10:0.5混合聚二甲基硅氧烷和硼酸粉，得到混合溶液，之后加入体积比为10:0.3的第一溶剂乙醇和催化剂盐酸，搅拌并升温至50℃后，加入去离子水，进行水解反应0.5h；在蒸馏装置中对水解产物进行减压蒸馏，进行温度为80℃的缩聚反应1h，得到含硼硅的包覆剂；
所述硼酸粉的纯度为99.9％；所述硼酸粉的粒径为30μm；所述催化剂的质量浓度为5mol/mL；所述水的添加量为硅氧烷和硼酸粉质量的2wt％；所述减压蒸馏的真空度为0.02MPa；
(2)按照质量比为0.5:10:1混合所述含硼硅的包覆剂、铁镍磁粉和第二溶剂丙酮，得到包覆后的软磁粉末；所述包覆后的软磁粉末还依次进行干燥和筛分处理；
(3)先混合所述包覆后的软磁粉末和粘结剂硅树脂，烘干处理后，再加入脱模剂硬脂酸锌，依次经压力为1500MPa的压制成型和氮气气氛中，温度为600℃的退火处理5h，得到硼硅包覆的金属软磁磁粉芯；所述包覆后的软磁粉末、粘结剂和脱模剂的质量比为10:0.05:0.05。
实施例2
本实施例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法包括如下步骤：
(1)先按照质量比为10:0.5混合聚二甲基硅氧烷和硼酸粉，得到混合溶液，之后加入体积比为10:0.3的第一溶剂乙醇和催化剂硫酸，搅拌并升温至80℃后，加入去离子水，进行水解反应5h；在蒸馏装置中对水解产物进行减压蒸馏，进行温度为100℃的缩聚反应1h，得到含硼硅的包覆剂；
所述硼酸粉的纯度为99.93％；所述硼酸粉的粒径为10μm；所述催化剂的质量浓度为2～10mol/mL；所述水的添加量为硅氧烷和硼酸粉质量的1～5wt％；所 述减压蒸馏的真空度为0.05MPa；
(2)按照质量比为0.05:10:1混合所述含硼硅的包覆剂、铁镍磁粉和第二溶剂丙酮，得到包覆后的软磁粉末；所述包覆后的软磁粉末还依次进行干燥和筛分处理；
(3)先混合所述包覆后的软磁粉末和粘结剂环氧树脂，烘干处理后，再加入脱模剂硬脂酸铝，依次经压力为1500MPa的压制成型和氮气气氛中，温度为650℃的退火处理2h，得到硼硅包覆的金属软磁磁粉芯；所述包覆后的软磁粉末、粘结剂和脱模剂的质量比为10:0.01:0.05。
实施例3
本实施例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法包括如下步骤：
(1)先按照质量比为10:0.5混合聚二甲基硅氧烷和硼酸粉，得到混合溶液，之后加入体积比为10:0.5的第一溶剂乙醇和催化剂硝酸，搅拌并升温至50℃后，加入去离子水，进行水解反应2h；在蒸馏装置中对水解产物进行减压蒸馏，进行温度为80℃的缩聚反应1h，得到含硼硅的包覆剂；
所述硼酸粉的纯度为99.95％；所述硼酸粉的粒径为25μm；所述催化剂的质量浓度为4mol/mL；所述水的添加量为硅氧烷和硼酸粉质量的4wt％；所述减压蒸馏的真空度为0.05MPa；
(2)按照质量比为0.05:10:1混合所述含硼硅的包覆剂、铁硅磁粉和第二溶剂丙酮，得到包覆后的软磁粉末；所述包覆后的软磁粉末还依次进行干燥和筛分处理；
(3)先混合所述包覆后的软磁粉末和粘结剂酚醛树脂，烘干处理后，再加入脱模剂石墨，依次经压力为1500MPa的压制成型和氮气气氛中，温度为700℃的退火处理7h，得到硼硅包覆的金属软磁磁粉芯；所述包覆后的软磁粉末、粘结剂和脱模剂的质量比为10:0.09:0.03。
实施例4
本实施例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法包括如下步骤：
(1)先按照质量比为10:0.5混合聚二甲基硅氧烷和硼酸粉，得到混合溶液，之后加入体积比为10:0.5的第一溶剂乙醇和催化剂硫酸，搅拌并升温至50℃后， 加入去离子水，进行水解反应5h；在蒸馏装置中对水解产物进行减压蒸馏，进行温度为120℃的缩聚反应6h，得到含硼硅的包覆剂；
所述硼酸粉的纯度为99.9％以上；所述硼酸粉的粒径为50μm；所述催化剂的质量浓度为10mol/mL；所述水的添加量为硅氧烷和硼酸粉质量的2.4wt％；所述减压蒸馏的真空度为0.1MPa；
(2)按照质量比为0.05:10:1混合所述含硼硅的包覆剂、铁硅铝磁粉和第二溶剂丙酮，得到包覆后的软磁粉末；所述包覆后的软磁粉末还依次进行干燥和筛分处理；
(3)先混合所述包覆后的软磁粉末和粘结剂环氧树脂，烘干处理后，再加入脱模剂硬脂酸锌，依次经压力为1500MPa的压制成型和氮气气氛中，温度为700℃的退火处理5.5h，得到硼硅包覆的金属软磁磁粉芯；所述包覆后的软磁粉末、粘结剂和脱模剂的质量比为10:0.08:0.01。
实施例5
本实施例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法包括如下步骤：
(1)先按照质量比为10:3混合二甲基二乙氧基硅烷和硼酸粉，得到混合溶液，之后加入体积比为10:0.1的第一溶剂甲醇和催化剂硝酸，搅拌并升温至100℃后，加入去离子水，进行水解反应5h；在蒸馏装置中对水解产物进行减压蒸馏，进行温度为150℃的缩聚反应20h，得到含硼硅的包覆剂；
所述硼酸粉的纯度为99.92％；所述硼酸粉的粒径为5μm；所述催化剂的质量浓度为2mol/mL；所述水的添加量为硅氧烷和硼酸粉质量的1wt％；所述减压蒸馏的真空度为0.02MPa；
(2)按照质量比为0.01:10:0.5混合所述含硼硅的包覆剂、铁硅磁粉和第二溶剂丙酮，得到包覆后的软磁粉末；所述包覆后的软磁粉末还依次进行干燥和筛分处理；
(3)先混合所述包覆后的软磁粉末和粘结剂硅树脂，烘干处理后，再加入脱模剂硬脂酸铝，依次经压力为1000MPa的压制成型和氮气气氛中，温度为500℃的退火处理8h，得到硼硅包覆的金属软磁磁粉芯；所述包覆后的软磁粉末、粘结剂和脱模剂的质量比为10:0.01:0.1。
实施例6
本实施例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法包括如下步骤：
(1)先按照质量比为10:0.5混合聚二甲基硅氧烷和硼酸粉，得到混合溶液，之后加入体积比为10:0.5的第一溶剂乙醇和催化剂硫酸，搅拌并升温至80℃后，加入去离子水，进行水解反应0.5h；在蒸馏装置中对水解产物进行减压蒸馏，进行温度为80℃的缩聚反应1h，得到含硼硅的包覆剂；
所述硼酸粉的纯度为99.98％；所述硼酸粉的粒径为50μm；所述催化剂的质量浓度为10mol/mL；所述水的添加量为硅氧烷和硼酸粉质量的5wt％；所述减压蒸馏的真空度为0.15MPa；
(2)按照质量比为0.5:10:1.5混合所述含硼硅的包覆剂、铁硅铝磁粉和第二溶剂丙酮，得到包覆后的软磁粉末；所述包覆后的软磁粉末还依次进行干燥和筛分处理；
(3)先混合所述包覆后的软磁粉末和粘结剂硅树脂，烘干处理后，再加入脱模剂硬脂酸锌，依次经压力为3000MPa的压制成型和氮气气氛中，温度为800℃的退火处理0.1h，得到硼硅包覆的金属软磁磁粉芯；所述包覆后的软磁粉末、粘结剂和脱模剂的质量比为10:0.1:0.5。
实施例7
本实施例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法除了将步骤(1)中硅氧烷和硼酸粉的质量比10:0.5替换为10:0.1外，其余均与实施例1相同。
实施例8
本实施例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法除了将步骤(1)中硅氧烷和硼酸粉的质量比10:0.5替换为10:4外，其余均与实施例1相同。
实施例9
本实施例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法除了将步骤(3)中压制成型的压力为1500MPa替换为500MPa外，其余均与实施例1相同。
实施例10
本实施例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法 除了将步骤(3)中压制成型的压力为1500MPa替换为3500MPa外，其余均与实施例1相同。
实施例11
本实施例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法除了将步骤(3)中退火处理的温度为600℃替换为400℃外，其余均与实施例1相同。
实施例12
本实施例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法除了将步骤(3)中退火处理的温度为600℃替换为900℃外，其余均与实施例1相同。
对比例1
本对比例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法包括如下步骤：
500目铁镍磁粉在磷酸中钝化，加入0.5wt％的高岭土绝缘包覆，再加入0.3wt％硅树脂进行二次包覆。在包覆后的磁粉中加入酚醛树脂作为粘结剂，硬脂酸锌作为脱模剂，在1500MPa下模压成型，并在氮气气氛下退火，退火温度为600℃，得到圆环样品。
对比例2
本对比例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法除了步骤(1)不加入硼酸粉外，其余均与实施例1相同。
对比例3
本对比例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法除了铁镍替换为铁硅磁粉，其余均与对比例1相同。
对比例4
本对比例提供一种硼硅包覆的金属软磁磁粉芯的制备方法，所述制备方法除了铁镍替换为铁硅铝磁粉，其余均与对比例1相同。
以上实施例和对比例得到硼硅包覆的金属软磁磁粉芯的磁导率和磁损耗结果如表1所示。
表1
从表1可以看出：
(1)综合实施例1～6可以看出，当原料为铁镍磁粉时，得到的硼硅包覆的金属软磁磁粉芯的磁导率可达125以上，在50kHz，100mT条件下，损耗可达133mW/cm3以下，在100kHz，100mT条件下，损耗可达287mW/cm3以下；当原料为铁硅磁粉时，得到的硼硅包覆的金属软磁磁粉芯的磁导率可达56以上，在50kHz，100mT条件下，损耗可达749mW/cm3以下，在100kHz，100mT条件下，损耗可达1783mW/cm3以下；当原料为铁硅铝磁粉时，得到的硼硅包覆的金属软磁磁粉芯的磁导率可达60以上，在50kHz，100mT条件下，损耗可达132mW/cm3以下，在100kHz，100mT条件下，损耗可达272mW/cm3以下；
(2)综合实施例1与实施例7～8可以看出，实施例7步骤(1)中硅氧烷和硼酸粉的质量比为10:0.1，得到的硼硅包覆的金属软磁磁粉芯的磁导率相比实施例1显著降低；但在50kHz，100mT条件下以及在100kHz，100mT条件下， 的损耗与实施例1相当；实施例8步骤(1)中硅氧烷和硼酸粉的质量比为10:4，得到的硼硅包覆的金属软磁磁粉芯的磁导率为132，磁导率略微提升，但损耗明显增加；
(3)综合实施例1与实施例9～10可以看出，实施例9步骤(3)中压制成型的压力较低，得到的硼硅包覆的金属软磁磁粉芯的磁导率较低，为76；实施例10步骤(3)中压制成型的压力较高，得到的硼硅包覆的金属软磁磁粉芯的磁导率比实施例1高，为141；但实施例9和10得到的硼硅包覆的金属软磁磁粉芯的损耗均比实施例1高很多；
(4)综合实施例1与实施例11～12可以看出，实施例11步骤(3)中退火处理的温度较低，得到的硼硅包覆的金属软磁磁粉芯的磁导率比实施例1略微降低，但损耗比实施例1高许多；实施例12步骤(3)中退火处理的温度较高，得到的硼硅包覆的金属软磁磁粉芯的磁导率与实施例1相当，但在100kHz，100mT条件下，损耗高达1210mW/cm3；
(5)综合实施例1与对比例1，实施例3、实施例5与对比例3，实施例4、实施例6与对比例4可以看出，本申请提供的硼硅包覆的金属软磁磁粉芯的制备方法应用于原料铁镍、铁硅、铁硅铝磁粉，相比对比例1、对比例3和对比例4的方法而言，得到的硼硅包覆的金属软磁磁粉芯的磁导率高且损耗低；
(6)综合实施例1与对比例2可以看出，对比例2的步骤(1)不加入硼酸粉，得到的金属软磁磁粉芯的磁导率比实施例1略低，但损耗远高于实施例1。
综上所述，本申请提供的硼硅包覆的金属软磁磁粉芯的制备方法采用特定的硅氧烷和硼酸粉的质量比，在特定的压制成型的压力和特定的退火处理的温度条件下，利用原料硼酸粉进行化学有机合成含硼硅包覆物，有效改善了金属软磁磁粉芯表面的绝缘包覆，提高了磁粉芯的电阻，得到的硼硅包覆的金属软磁磁粉芯的磁性能优越，磁导率高且磁损耗低。
申请人声明，以上所述仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，均落在本申请的保护范围和公开范围之内。

Claims (13)

  1. 一种硼硅包覆的金属软磁磁粉芯的制备方法，其包括如下步骤：
    (1)混合硅氧烷、硼酸粉、第一溶剂、催化剂和水，进行水解反应，水解产物经缩聚反应，得到含硼硅的包覆剂；
    (2)混合所述含硼硅的包覆剂、软磁粉末和第二溶剂，得到包覆后的软磁粉末；
    (3)混合所述包覆后的软磁粉末、粘结剂和脱模剂，依次经压制成型和退火处理，得到硼硅包覆的金属软磁磁粉芯。
  2. 根据权利要求1所述的制备方法，其中，步骤(1)所述混合硅氧烷、硼酸粉、第一溶剂、催化剂和水的步骤包括：先混合硅氧烷和硼酸粉，得到混合溶液，之后加入第一溶剂和催化剂，搅拌并升温至50～100℃后，加入水。
  3. 根据权利要求1或2所述的制备方法，其中，步骤(1)所述硅氧烷包括聚二甲基硅氧烷和/或二甲基二乙氧基硅烷。
  4. 根据权利要求1～3任一项所述的制备方法，其中，所述硼酸粉的纯度为99.9％以上。
  5. 根据权利要求1～4任一项所述的制备方法，其中，所述硼酸粉的粒径为5～50μm。
  6. 根据权利要求1～5任一项所述的制备方法，其中，所述硅氧烷和硼酸粉的质量比为10:(0.5～3)。
  7. 根据权利要求1～6任一项所述的制备方法，其中，步骤(1)所述第一溶剂包括甲醇、乙醇、异丙醇或正丁醇中的任意一种或至少两种的组合；
    优选地，所述催化剂包括盐酸、硫酸或硝酸中的任意一种或至少两种的组合；
    优选地，所述催化剂的质量浓度为2～10mol/mL；
    优选地，所述第一溶剂和催化剂的体积比为10:(0.1～0.5)；
    优选地，所述水包括去离子水；
    优选地，所述水的添加量为硅氧烷和硼酸粉质量的1～5％；
    优选地，所述水解反应的时间为0.5～5h。
  8. 根据权利要求1～7任一项所述的制备方法，其中，步骤(1)所述缩聚反应在蒸馏装置中进行；
    优选地，在所述蒸馏装置中对水解产物进行减压蒸馏；
    优选地，所述减压蒸馏的真空度为0.02～0.15MPa；
    优选地，所述缩聚反应的温度为80～150℃；
    优选地，所述缩聚反应的时间为1～20h。
  9. 根据权利要求1～8任一项所述的制备方法，其中，步骤(2)所述含硼硅的包覆剂、软磁粉末和第二溶剂的质量比为(0.01～0.5):10:(0.5～1.5)；
    优选地，所述软磁粉末包括铁镍磁粉、铁硅磁粉、铁硅铝磁粉、铁镍钼磁粉、非晶磁粉或纳米晶磁粉中的任意一种或至少两种的组合；
    优选地，所述第二溶剂包括丙酮；
    优选地，所述包覆后的软磁粉末还依次进行干燥和筛分处理。
  10. 根据权利要求1～8任一项所述的制备方法，其中，步骤(3)混合所述包覆后的软磁粉末、粘结剂和脱模剂的步骤包括：先混合所述包覆后的软磁粉末和粘结剂，烘干处理后，再加入脱模剂；
    优选地，所述包覆后的软磁粉末、粘结剂和脱模剂的质量比为10:(0.01～0.1):(0.01～0.1)；
    优选地，所述粘结剂包括硅树脂、环氧树脂或酚醛树脂中的任意一种或至少两种的组合；
    优选地，所述脱模剂包括硬脂酸锌、硬脂酸铝或石墨中的任意一种或至少两种的组合。
  11. 根据权利要求1～10任一项所述的制备方法，其中，步骤(3)所述压制成型的压力为1000～3000MPa；
    优选地，所述退火处理在氮气气氛中进行；
    优选地，所述退火处理的温度为500～800℃；
    优选地，所述退火处理的时间为0.1～8h。
  12. 根据权利要求1～11任一项所述的制备方法，其包括如下步骤：
    (1)先按照质量比为10:(0.5～3)混合硅氧烷和硼酸粉，得到混合溶液，之后加入体积比为10:(0.1～0.5)的第一溶剂和催化剂，搅拌并升温至50～100℃后，加入水，进行水解反应0.5～5h；在蒸馏装置中对水解产物进行减压蒸馏，进行温度为80～150℃的缩聚反应1～20h，得到含硼硅的包覆剂；
    所述硅氧烷包括聚二甲基硅氧烷和/或二甲基二乙氧基硅烷；所述硼酸粉的纯度为99.9％以上；所述硼酸粉的粒径为5～50μm；所述第一溶剂包括甲醇、乙 醇、异丙醇或正丁醇中的任意一种或至少两种的组合；所述催化剂包括盐酸、硫酸或硝酸中的任意一种或至少两种的组合；所述催化剂的质量浓度为2～10mol/mL；所述水包括去离子水；所述水的添加量为硅氧烷和硼酸粉质量的1～5wt％；所述减压蒸馏的真空度为0.02～0.15MPa；
    (2)按照质量比为(0.01～0.5):10:(0.5～1.5)混合所述含硼硅的包覆剂、软磁粉末和第二溶剂，得到包覆后的软磁粉末；
    所述软磁粉末包括铁镍磁粉、铁硅磁粉、铁硅铝磁粉或铁镍钼磁粉中的任意一种或至少两种的组合；所述第二溶剂包括丙酮；所述包覆后的软磁粉末还依次进行干燥和筛分处理；
    (3)先混合所述包覆后的软磁粉末和粘结剂，烘干处理后，再加入脱模剂，依次经压力为1000～3000MPa的压制成型和氮气气氛中，温度为500～800℃的退火处理0.1～8h，得到硼硅包覆的金属软磁磁粉芯；
    所述包覆后的软磁粉末、粘结剂和脱模剂的质量比为10:(0.01～0.1):(0.01～0.1)；所述粘结剂包括硅树脂、环氧树脂或酚醛树脂中的任意一种或至少两种的组合；所述脱模剂包括硬脂酸锌、硬脂酸铝或石墨中的任意一种或至少两种的组合。
  13. 一种硼硅包覆的金属软磁磁粉芯，其中，所述金属软磁磁粉芯由权利要求1～12任一项所述的硼硅包覆的金属软磁磁粉芯的制备方法制得。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140232507A1 (en) * 2011-10-03 2014-08-21 Panasonic Corporation Powder magnetic core and production method for same
CN110246679A (zh) * 2019-07-31 2019-09-17 合肥工业大学 一种基于有机/无机复合绝缘工艺的金属软磁粉芯制备方法
CN113072812A (zh) * 2021-04-22 2021-07-06 西安理工大学 铁酸钴磁性纳米颗粒填充应变率敏感型复合材料及方法
CN115621029A (zh) * 2022-10-28 2023-01-17 横店集团东磁股份有限公司 一种硼硅包覆的金属软磁磁粉芯及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140232507A1 (en) * 2011-10-03 2014-08-21 Panasonic Corporation Powder magnetic core and production method for same
CN110246679A (zh) * 2019-07-31 2019-09-17 合肥工业大学 一种基于有机/无机复合绝缘工艺的金属软磁粉芯制备方法
CN113072812A (zh) * 2021-04-22 2021-07-06 西安理工大学 铁酸钴磁性纳米颗粒填充应变率敏感型复合材料及方法
CN115621029A (zh) * 2022-10-28 2023-01-17 横店集团东磁股份有限公司 一种硼硅包覆的金属软磁磁粉芯及其制备方法

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