WO2020009303A1 - 하이브리드 자성 섬유 및 그 제조방법 - Google Patents

하이브리드 자성 섬유 및 그 제조방법 Download PDF

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Publication number
WO2020009303A1
WO2020009303A1 PCT/KR2019/001363 KR2019001363W WO2020009303A1 WO 2020009303 A1 WO2020009303 A1 WO 2020009303A1 KR 2019001363 W KR2019001363 W KR 2019001363W WO 2020009303 A1 WO2020009303 A1 WO 2020009303A1
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Prior art keywords
magnetic
hybrid
hybrid magnetic
fiber
rare earth
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PCT/KR2019/001363
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English (en)
French (fr)
Korean (ko)
Inventor
좌용호
김종렬
이지민
황태연
강민규
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Industry University Cooperation Foundation IUCF HYU
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Industry University Cooperation Foundation IUCF HYU
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Priority claimed from KR1020190011806A external-priority patent/KR102125168B1/ko
Application filed by Industry University Cooperation Foundation IUCF HYU filed Critical Industry University Cooperation Foundation IUCF HYU
Priority to EP19830775.3A priority Critical patent/EP3819924A4/de
Publication of WO2020009303A1 publication Critical patent/WO2020009303A1/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • H01F41/0253—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 for manufacturing permanent magnets
    • H01F41/0273—Imparting anisotropy
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
    • H01F1/0072—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity one dimensional, i.e. linear or dendritic nanostructures
    • 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
    • H01F1/032—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 hard-magnetic materials
    • H01F1/04—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 hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • 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
    • 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
    • H01F1/032—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 hard-magnetic materials
    • H01F1/04—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 hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/0553—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 obtained by reduction or by hydrogen decrepitation or embrittlement
    • 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
    • H01F1/032—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 hard-magnetic materials
    • H01F1/04—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 hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0579—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B with exchange spin coupling between hard and soft nanophases, e.g. nanocomposite spring magnets
    • 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
    • H01F1/143—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 wires

Definitions

  • the present invention relates to a hybrid magnetic fiber and a method of manufacturing the same, and relates to a hybrid magnetic fiber including both hard magnetic and soft magnetic and a method of manufacturing the same.
  • the hard magnetic permanent magnets which are widely applied to the electric and motor industries, are largely divided into rare earth-based magnets, and non-rare earth magnets such as ferrite and alnico.
  • Rare earth magnets refer to compounds between rare earth metals and transition metals, and have a higher maximum magnetic energy ((BH) max) value than non-rare earth permanent magnets, which are essential to keep up with the recent weight reduction, miniaturization, and high performance of electronic products. It is an indispensable material.
  • BH maximum magnetic energy
  • Korean Patent Publication No. 10-2017-0108468 (Application No .: 10-2016-0032417, Applicant: Yonsei University Industry-Academic Cooperation Foundation) includes a substrate, and a laminate formed on the substrate and formed of a Bi thin film layer and an Mn thin film layer.
  • a coercive force-improved non-rare earth permanent magnet including a thin film laminate obtained by repeatedly laminating and heat-treating a unit at least two times and a method of manufacturing the same.
  • One technical problem to be solved by the present invention is to provide a hybrid magnetic fiber with improved coercivity and saturation magnetization and a method of manufacturing the same.
  • Another technical problem to be solved by the present invention is to provide a hybrid magnetic fiber having an improved maximum magnetic energy value and a method of manufacturing the same.
  • Another technical problem to be solved by the present invention is to provide a hybrid magnetic fiber with a reduced amount of rare earth and a method of manufacturing the same.
  • the technical problem to be solved by the present invention is not limited to the above.
  • the present invention provides a hybrid magnetic fiber manufacturing method.
  • the method of manufacturing a hybrid magnetic fiber may include preparing a source solution including a first source material including a rare earth element and a second source material including a transition metal element, and electrospinning the source solution. Forming a preliminary hybrid magnetic fiber comprising a rare earth oxide and a transition metal oxide, and reducing the preliminary hybrid magnetic fiber to form a magnetic crystal comprising a compound of the rare earth element and the transition metal element, And forming a hybrid magnetic fiber including a magnetic boundary layer including the transition metal element.
  • the magnetic crystal may include a hard-magnetic property
  • the magnetic boundary layer may include a soft-magnetic property
  • the magnetic boundary layer may include following the magnetization behavior of the magnetic crystal.
  • the mole fraction of the rare earth element in the source solution may include more than 9.290 at% and less than 10.562 at%.
  • the forming of the hybrid magnetic fibers may include mixing the preliminary hybrid magnetic fibers with a reducing agent, heat treating the preliminary hybrid magnetic fibers mixed with the reducing agent, and heat treating the preliminary hybrid magnetic fibers. It may include the step of washing with a washing solution.
  • the preliminary hybrid magnetic fiber mixed with the reducing agent may include heat treatment at a temperature of more than 500 ° C. and less than 800 ° C.
  • the reducing agent may include calcium (Ca).
  • the washing solution may include at least one of ammonium chloride (NH 4 Cl), and methanol (CH 3 OH).
  • the source solution may further include a crystallization source including a metal and a viscous source including a polymer.
  • the rare earth element may include any one of La, Ce, Pr, Nd, Sm, or Gd.
  • the transition metal element may include any one of Fe, Co, or Ni.
  • the present invention provides a hybrid magnetic fiber.
  • the hybrid magnetic fibers may be disposed between a plurality of magnetic crystals including a rare earth element and a compound of a transition metal element, and the magnetic crystals adjacent to each other to surround the magnetic crystals, It may include a magnetic boundary layer (magnetic boundary layer) containing the transition metal element.
  • the volume fraction of the magnetic boundary layer may include more than 0 vol% less than 10 vol%.
  • the magnetic crystal may have a hard magnetic property
  • the magnetic boundary layer may have a soft magnetic property
  • the magnetic boundary layer may include a magnetization behavior of the magnetic crystal.
  • a method of manufacturing a hybrid magnetic fiber preparing a source solution including a first source material including a rare earth element, and a second source material including a transition metal element, the source solution Electrospinning to form a preliminary hybrid magnetic fiber comprising a rare earth oxide and a transition metal oxide, and reducing the preliminary hybrid magnetic fiber to include a compound of the rare earth element and the transition metal element, and to exhibit hard magnetic properties.
  • the method may include forming a hybrid magnetic fiber having a magnetic crystal having a magnetic crystal and a magnetic boundary layer including the transition metal element and having soft magnetic properties.
  • the volume fraction of the magnetic boundary layer in the hybrid magnetic fiber is controlled, as a result of the magnetic crystal And a magnetic exchange coupling effect between the magnetic boundary layers. Accordingly, saturation magnetization is increased while maintaining high coercivity, and further, the maximum magnetic energy ((BH) max) value is improved to provide a hybrid magnetic fiber exhibiting excellent magnetic properties. Can be.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a hybrid magnetic fiber according to an embodiment of the present invention.
  • FIG. 2 is a flowchart illustrating a hybrid magnetic fiber forming step of the hybrid magnetic fiber manufacturing method according to an embodiment of the present invention in detail.
  • FIG 3 is a view showing a manufacturing process of a hybrid magnetic fiber according to an embodiment of the present invention.
  • FIG. 4 is a view showing a hybrid magnetic fiber according to an embodiment of the present invention.
  • 5 is a graph showing the characteristics of soft and hard magnetic materials.
  • FIG. 6 is a graph showing characteristics in the case where the self-exchange coupling effect is exhibited between soft magnetic and hard magnetic materials.
  • Example 12 is a photograph comparing the influence of the washing solution in the process of washing the hybrid magnetic fiber according to Example 1 of the present invention.
  • Example 13 is a photograph of a hybrid magnetic fiber according to Example 2 of the present invention.
  • Example 15 is a graph showing the effect of the mole fraction of rare earth elements contained in the source solution on the structure of the hybrid magnetic fiber according to Example 2 of the present invention.
  • 16 and 17 are graphs showing the effect of the mole fraction of the rare earth elements contained in the source solution on the structure of the hybrid magnetic fiber according to Example 1 of the present invention.
  • FIG. 18 is a graph showing the characteristics of a hybrid magnetic fiber according to a comparative example of the present invention in which no magnetic exchange coupling effect occurs.
  • Example 19 is a graph showing the effect of the volume fraction of the magnetic boundary layer on the magnetic properties of the hybrid magnetic fiber according to Example 1 of the present invention.
  • Example 20 is a graph showing the effect of the volume fraction of the magnetic crystals on the residual magnetization value of the hybrid magnetic fiber according to Example 1 of the present invention.
  • 21 is a graph showing the effect of the volume fraction of the magnetic crystal on the maximum magnetic energy value of the hybrid magnetic fiber according to Example 1 of the present invention.
  • 22 and 23 are graphs showing modification of the Recoil curve of the hybrid magnetic fibers according to Example 1 of the present invention, in which the volume fractions of the magnetic crystals and the magnetic crystal layers are different.
  • Example 24 is a graph showing Recoil susceptibility values of hybrid magnetic fibers according to Example 1 of the present invention, in which the volume fractions of the magnetic boundary layers are different from each other.
  • 25 to 27 is a graph comparing the characteristics of the heat treatment in the process of producing a hybrid magnetic fiber according to Example 1 of the present invention.
  • 29 to 31 are photographs and graphs comparing the diameters of the hybrid magnetic fibers according to Examples 1 and 3 of the present invention.
  • first, second, and third are used to describe various components, but these components should not be limited by these terms. These terms are only used to distinguish one component from another. Thus, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment.
  • first component in one embodiment may be referred to as a second component in another embodiment.
  • second component in another embodiment.
  • Each embodiment described and illustrated herein also includes its complementary embodiment.
  • the term 'and / or' is used herein to include at least one of the components listed before and after.
  • connection is used herein to mean both indirectly connecting a plurality of components, and directly connecting.
  • FIG. 1 is a flow chart illustrating a method of manufacturing a hybrid magnetic fiber according to an embodiment of the present invention
  • Figure 2 is a flow chart illustrating the hybrid magnetic fiber forming step of the hybrid magnetic fiber manufacturing method according to an embodiment of the present invention in detail.
  • 3 is a view showing a hybrid magnetic fiber manufacturing process according to an embodiment of the present invention
  • Figure 4 is a view showing a hybrid magnetic fiber according to an embodiment of the present invention.
  • a source solution including a first source material and a second source material may be prepared (S100).
  • the first source material may include a rare-earth element.
  • the rare earth element may include any one of La, Ce, Pr, Nd, Sm, or Gd.
  • the second source material may include a transition-metal element.
  • the transition metal element may include any one of Fe, Co, or Ni.
  • the source solution may further include a crystallization source, and a viscous source.
  • the crystallization source may include a metal.
  • the metal may be a metal water-soluble salt such as copper (Cu) or zirconium (Zr).
  • the crystallization source can improve the crystallinity of the hybrid magnetic fiber 100 to be described later.
  • the viscous source may include a polymer.
  • the polymer may include at least one of polyvinylpyrrolidone (PVP), polyacrylonitrile (PAN), poly (vinyl acetate) (PVAC), polyvinylbutyral (PVB), poly (vinyl alcohol) (PVA), or polyethylene oxide (PEO). It may include.
  • the viscous source may give viscosity to the source solution and control the diameter of the hybrid magnetic fiber 100 to be described later.
  • the mole fraction (at%) of the rare earth element in the source solution can be controlled. Specifically, the mole fraction of the rare earth element in the source solution may be controlled to be greater than 9.290 at% and less than 10.562 at%. In this case, an exchange-coupling effect may be generated between the magnetic crystal 110 and the magnetic boundary layer 120, which are included in the hybrid magnetic fiber 100 to be described later. In addition, the mole fraction of the rare earth element in the source solution may be controlled to more than 10.156 at% and less than 10.562 at%. In this case, the magnetic exchange coupling effect generated between the magnetic crystal 110 and the magnetic boundary layer 120 included in the hybrid magnetic fiber 100 to be described later may have a maximum value. A more detailed description will be given later.
  • the source solution is electrospun to form a preliminary hybrid magnetic fiber (S200).
  • the preliminary hybrid magnetic fiber formed by electrospinning the source solution may include a rare earth oxide and a transition metal oxide.
  • the preliminary hybrid magnetic fiber forming step may include a first preliminary hybrid magnetic fiber forming step and a second preliminary hybrid magnetic fiber forming step.
  • the first preliminary hybrid magnetic fiber forming step may be performed by electrospinning the source solution.
  • the first preliminary hybrid magnetic fiber may be made of a solid component of the source solution.
  • the first preliminary hybrid magnetic fiber may include a water-soluble metal salt, a polymer, and the like.
  • the forming of the second preliminary hybrid magnetic fiber may be performed by calcining the first preliminary hybrid magnetic fiber. That is, the first preliminary hybrid magnetic fiber may be thermally treated to decompose an organic material including a polymer in the first preliminary hybrid magnetic fiber.
  • the second preliminary hybrid magnetic fiber may include an oxide including all of a rare earth oxide, a transition metal oxide, and a rare earth-transition metal.
  • the source solution may be injected into a syringe 10, and the source solution may be spun by using a syringe pump 20.
  • the tip 30 of the syringe has an inner diameter of 0.05 to 2 mm
  • a collector in which the syringe tip 30 and the preliminary hybrid magnetic fibers are collected is spaced 10 to 20 cm apart
  • the syringe pump 20 May spin the source solution at a rate of 0.3-0.8 mL / h.
  • the voltage applied for electrospinning may be 16-23 kV.
  • the first preliminary hybrid magnetic fiber may be formed through the above-described process.
  • the first preliminary hybrid magnetic fiber may be collected in an alumina crucible and heat-treated at atmospheric pressure of 500 to 900 ° C. in an atmospheric atmosphere. In this process, all organic materials including polymers can be thermally decomposed. At this time, the temperature increase rate condition may be 1 ⁇ 10 °C per minute.
  • the second preliminary hybrid magnetic fiber may be formed through the above-described process.
  • the preliminary hybrid magnetic fibers may be reduced to form a hybrid magnetic fiber 100 including a magnetic crystal 110 and a magnetic boundary layer 120 (S300).
  • the hybrid magnetic fiber 100 includes a plurality of the magnetic crystals 110, the magnetic boundary layer 120 is disposed between the magnetic crystals 110 adjacent to each other, the magnetic crystals It may have a structure surrounding the (110).
  • the magnetic crystal 110 may include a compound of the rare earth element and the electrometal element.
  • the magnetic crystal 110 may include Nd 2 Fe 14 B, Sm 2 Co 17 and the like. Accordingly, the magnetic crystal 110 may have a hard-magnetic characteristic.
  • the magnetic boundary layer 120 may include the transition metal element.
  • the magnetic boundary layer 120 may include fcc-Fe, fcc-Co, and the like. Accordingly, the magnetic boundary layer 120 may have a soft magnetic property.
  • the hybrid magnetic fiber 100 is a chain in which the first single crystal 110 of hard magnetic properties and the second single crystal 120 of soft magnetic properties are alternately and repeatedly arranged. It may have a structure.
  • the hybrid magnetic fiber 100 has a structure of any one of the magnetic crystal 110-magnetic boundary layer 120 structure, or the first single crystal 110-second single crystal 120 chain structure.
  • the structure of the hybrid magnetic fiber 100, the conditions of the electrospinning process described above, the heat treatment conditions in the heat treatment reduction step described below, and the hard magnetic material, and soft magnetic material in the hybrid magnetic fiber 100 It can be determined according to the volume ratio and the like. Specifically, when controlled by the conditions of the electrospinning process, when the diameter of the hybrid magnetic fiber 100 is less than 500nm, the hybrid magnetic fiber 100 is the first single crystal 110-second single crystal 120 ) Can be formed into a chain structure. In addition, when the volume of the soft magnetic material is 10 vol% or more in the hybrid magnetic fiber 100, the hybrid magnetic fiber 100 may be formed in a first single crystal 110-second single crystal 120 chain structure. Can be.
  • the hybrid magnetic fibers 100 may have different industrial fields depending on the type of structure to be formed.
  • the hybrid magnetic fiber 100 may be sintered to be used in a high output product in the form of a sintered magnet.
  • it can be used in various advanced commercial equipment such as driving motors of hybrid vehicles (HEV) and electric vehicles (EVs), small motors for vehicles, VCMs for hard disks, speakers for mobile phones, small parts in industrial robots, and MRI.
  • HEV hybrid vehicles
  • EVs electric vehicles
  • small motors for vehicles small motors for vehicles
  • VCMs for hard disks
  • speakers for mobile phones small parts in industrial robots
  • MRI magnetic resonance imaging
  • the hybrid magnetic fiber 100 has a first single crystal 110-second single crystal 120 chain structure
  • the hybrid magnetic fiber 100 is mixed with a binder material and molded to form a bond-based magnet ( Plastic magnet, rubber magnet).
  • a bond-based magnet Plastic magnet, rubber magnet
  • the magnetic properties are lower than that of the sintered magnet, it can be used for door packing of a refrigerator, paperweight of a bulletin board, various stationery, etc. due to its high workability, seismic resistance, and impact resistance.
  • the forming of the hybrid magnetic fiber 100 (S300), the step of mixing the preliminary hybrid magnetic fiber with a reducing agent (S310), the step of heat-treating the preliminary hybrid magnetic fiber mixed with the reducing agent ( S320), and washing the heat-treated preliminary hybrid magnetic fiber with a washing solution (S330). That is, after the preliminary hybrid magnetic fiber 100 is mixed with a reducing agent and heat-treated, the hybrid magnetic fiber 100 may be formed.
  • the reducing agent may include calcium (Ca).
  • the reducing agent may include CaH 2 .
  • the hybrid magnetic fiber 100 may be easily formed.
  • rare earth elements it has a very small oxidation energy, it is possible to maintain the most stable phase in the form of oxides. Accordingly, in order to reduce the rare earth oxide to metal, a high temperature of 1500 ° C. or higher and a hydrogen atmosphere are required, and process difficulties are generated.
  • calcium (Ca) has a smaller oxidation energy than rare earth elements, when used as a reducing agent, a relatively low heat treatment temperature (for example, 500 to 800 ° C.) and a rare earth oxide in a non-hydrogen atmosphere are used. Can be easily reduced.
  • the heat treatment temperature of the preliminary hybrid magnetic fiber mixed with the reducing agent may be controlled. Specifically, the preliminary hybrid magnetic fiber mixed with the reducing agent may be heat-treated at a temperature of more than 500 °C less than 800 °C. In this case, the hybrid magnetic fiber 100 may be easily formed. On the contrary, when the preliminary hybrid magnetic fiber mixed with the reducing agent is heat-treated at a temperature of 500 ° C. or less, a problem may occur in which the reduction is not performed because the temperature is too low. In addition, when the preliminary hybrid magnetic fiber mixed with the reducing agent is heat-treated at a temperature of 800 ° C. or more, the hybrid magnetic fiber 100 may not be in the form of a fiber and may be deformed into a particle form.
  • the washing solution may include at least one of ammonium chloride (NH 4 Cl), and methanol (CH 3 OH).
  • the hybrid magnetic fiber 100 may be easily formed.
  • a reducing agent including calcium (Ca) calcium oxide (CaO) may be formed on the metal surface of which the rare earth oxide is reduced. Accordingly, a process for removing calcium oxide (CaO) is required, and a conventional calcium oxide (CaO) removing process uses a washing solution in which acetic acid or hydrochloric acid is mixed with ultrapure water.
  • a problem may occur when the acid solution causes a fatal effect such as corrosion or oxidation even on the magnetic phase.
  • the washing solution containing at least one of ammonium chloride (NH 4 Cl) and methanol (CH 3 OH) calcium oxide (CaO) can be easily removed without affecting the magnetic phase. .
  • the volume fraction (vol%) of the magnetic boundary layer 120 may be controlled. Specifically, in the hybrid magnetic fiber 100, the volume fraction of the magnetic boundary layer 120 may be controlled to more than 0 vol% less than 10 vol%. In this case, the magnetic boundary layer 120 may follow the magnetization behavior of the magnetic crystal 110. That is, an exchange-coupling effect may be generated between the magnetic crystal 110 and the magnetic boundary layer 120. In addition, in the hybrid magnetic fiber 100, the volume fraction of the magnetic boundary layer 120 may be controlled to more than 0 vol% less than 3 vol%. In this case, the magnetic exchange coupling effect generated between the magnetic crystal 110 and the magnetic boundary layer 120 may have a maximum value.
  • Figure 6 is a graph showing the characteristics when the magnetic exchange coupling effect between the soft magnetic and hard magnetic material.
  • the hybrid magnetic fiber 100 As described above, the hybrid magnetic fiber 100 according to the embodiment, the magnetic crystal 110 of the hard magnetic properties included in the hybrid magnetic fiber 100, and the magnetic boundary layer 120 of the soft magnetic properties A self-exchange effect may occur between them.
  • the volume fraction of the magnetic boundary layer 120 in the hybrid magnetic fiber 100 can be controlled.
  • the volume fraction of the magnetic boundary layer 120 in the hybrid magnetic fiber 100 may be controlled by the mole fraction of the rare earth element in the source solution.
  • the mole fraction of the rare earth element in the source solution according to the volume fraction of the magnetic boundary layer 120 in the hybrid magnetic fiber 100 may be calculated through Equation 1 below.
  • the volume fraction of the magnetic boundary layer 120 in the hybrid magnetic fiber 100 is controlled, resulting in the magnetic crystal 110 and the magnetic boundary layer.
  • a self-exchange coupling effect between 120 may occur.
  • the mole fraction of the rare earth element in the source solution is controlled to be greater than 9.290 at% and less than 10.562 at%
  • the volume fraction of the magnetic boundary layer 120 in the hybrid magnetic fiber 100 is greater than 0 vol% 10. It can be controlled to less than vol%.
  • a magnetic exchange coupling effect may occur between the magnetic crystal 110 and the magnetic boundary layer 120.
  • the hybrid magnetic fiber 100 according to the embodiment exhibits a high magnetic property, it can be easily used as a permanent magnet.
  • the hybrid magnetic fiber 100 according to the embodiment may exhibit high magnetic properties through the mixing of the hard magnetic material and the soft magnetic material, so that the use of the rare earth material for manufacturing the permanent magnet may be reduced. Can be.
  • a soft-magnetic material is coated on the hard magnetic material to form a core-shell structured material.
  • a sol-gel coating method is used.
  • nano-powders such as chemical reaction of hard magnetic material in air and hydrogen heat treatment for sol formation and reduction, oxidation of demagnetizing material in heat treatment to remove organic matter, etc. Since it is very susceptible to surface oxidation, ferrite in the form of oxide is mainly used. Accordingly, there is a problem that it is difficult to expect higher magnetic properties than commercial hard magnetic materials.
  • a composite powder is prepared by coating a soft magnetic material on the surface of a hard magnetic material by electroless or electrolytic deposition.
  • a process of dipping a light magnetic material in an acid solution containing hydrochloric acid (HCl) and ammonia solution Oxidation and surface defects of the hard magnetic material may be generated from the process of using the basic plating solution. Accordingly, the use of the ferrite in a stable oxide form is limited, and when the soft magnetic coating layer prepared as a result of the deposition is an oxide, there is a problem that an additional reduction heat treatment process must be accompanied.
  • the method of manufacturing a hybrid magnetic fiber preparing a source solution comprising a first source material containing a rare earth element, and a second source material containing a transition metal element, the Electrospinning a source solution to form the preliminary hybrid magnetic fiber comprising a rare earth oxide and a transition metal oxide, and reducing the preliminary hybrid magnetic fiber to include a compound of the rare earth element and the transition metal element, Forming the hybrid magnetic fiber 100 including the magnetic crystal 110 having a hard magnetic property and the magnetic boundary layer 120 including the transition metal element and having a soft magnetic property. It may include the step.
  • the volume fraction of the magnetic boundary layer 120 in the hybrid magnetic fiber 100 is controlled by controlling the mole fraction of the rare earth element in the source solution.
  • a magnetic exchange coupling effect may be generated between the magnetic crystal 110 and the magnetic boundary layer 120. Accordingly, saturation magnetization is increased while maintaining high coercivity, and further, the maximum magnetic energy ((BH) max) value is improved to provide a hybrid magnetic fiber exhibiting excellent magnetic properties. Can be.
  • the prepared source solution is placed in a syringe for electrospinning and continuously pushed at a rate of 0.3 to 0.8 mL / h using a syringe pump.
  • the tip of the syringe and the collector in which the spun fibers are collected are spaced apart at intervals of 15 cm, and a high voltage (16-23 kV) is applied so that the source solution is spun by the potential difference.
  • the material deposited on the collector is collected in an alumina (alumina, Al 2 O 3 ) crucible and heat treated at an air temperature of about 700 ° C. for 3 hours to decompose all organic materials including polymers.
  • the rare earth-containing oxide of SmCoO 3 -Co 3 O 4 - a spare magnetic hybrid fibers comprising a transition metal oxide can be obtained.
  • the preliminary hybrid magnetic fibers were mixed with CaH 2 in a volume ratio of 1: 1 and reduced by heat treatment for 3 hours at a temperature of about 700 ° C. in an inert atmosphere, followed by washing with ammonium chloride and methanol to give Sm of hard magnetic properties.
  • a hybrid magnetic fiber according to the first embodiment including a 2 Co 17 magnetic crystal and a fcc-Co magnetic boundary layer having soft magnetic properties was prepared.
  • boric acid (H 3 BO 3 ) was further mixed as much as half the number of moles of neodymium (III) nitrate hexahydrate.
  • the prepared source solution is placed in a syringe for electrospinning and continuously pushed at a rate of 0.3 to 0.8 mL / h using a syringe pump.
  • the tip of the syringe and the collector in which the spun fibers are collected are spaced at an interval of 18 cm, and a high voltage (16-23 kV) is applied so that the source solution is spun by the potential difference.
  • the material deposited on the collector is collected in an alumina (alumina, Al 2 O 3 ) crucible and heat treated at an air temperature of about 700 ° C. for 3 hours to decompose all organic materials including polymers.
  • a preliminary hybrid magnetic fiber containing a rare earth oxide-transition metal oxide of NdFeO 3 -NdBO 3 -Fe 2 O 3 is obtained.
  • the preliminary hybrid magnetic fibers were mixed with CaH 2 in a volume ratio of 1: 1 and reduced by heat treatment for 3 hours at a temperature of about 700 ° C. in an inert atmosphere, followed by washing with ammonium chloride and methanol to give Nd of hard magnetic properties.
  • a hybrid magnetic fiber according to a second embodiment including a 2 Fe 14 B magnetic crystal and a fcc-Fe magnetic boundary layer having soft magnetic properties was prepared.
  • a hybrid magnetic fiber according to Example 1 was prepared, but manufactured to have a diameter of 250 nm or less, thereby preparing a hybrid magnetic fiber according to Example 3 having a chain structure of hard magnetic property single crystal-soft magnetic property single crystal.
  • the hybrid magnetic fiber according to Example 1 wherein the mole fraction of the rare earth element in the source solution is controlled to 10.56 at%, 0 at%, 9.91 at%, and 4.80 at%, is SEM Scanning electron microscope images were taken and shown in FIGS. 7A, 7B, 8A, and 8B, respectively. As shown in FIG. 7 and FIG. 8, it was confirmed that the hybrid magnetic fiber according to Example 1 was formed in a fiber shape having a diameter of about 500 nm.
  • the temperature according to the heat treatment in the reduction step of the preliminary hybrid magnetic fiber is controlled to 400 °C, 500 °C, 600 °C, 700 °C, 750 °C, and 800 °C the hybrid according to Example 1 formed SEM images of the magnetic fibers were carried out in FIGS. 9A, 9B, 10A, 10B, 11A, and 11B, respectively. Indicated.
  • Example 12 is a photograph comparing the influence of the washing solution in the process of washing the hybrid magnetic fiber according to Example 1 of the present invention.
  • Example 13 is a photograph of a hybrid magnetic fiber according to Example 2 of the present invention.
  • FIG. 14 the state of the Sm-Co compound according to the mole fraction (at%) and temperature (° C.) of Sm in the Sm-Co compound is shown. As can be seen in Figure 14, when the mole fraction of Sm in the Sm-Co compound is less than 10.6 at%, it was confirmed that the hard magnetic properties and soft magnetic properties coexist.
  • Example 15 is a graph showing the effect of the mole fraction of rare earth elements contained in the source solution on the structure of the hybrid magnetic fiber according to Example 2 of the present invention.
  • the hybrid magnetic material according to Example 2 wherein the mole fraction of the rare earth element Nd in the source solution is controlled to 12.5 at%, 3.18 at%, and 0 at%, is formed.
  • X-ray diffraction analysis was shown by measuring the relative intensity (au) according to 2 ⁇ (degree) for each fiber.
  • FIG. 15 (a) when the mole fraction of the rare earth element in the source solution is 12.5 at%, only the hard magnetic properties of Nd 2 Fe 14 B were found.
  • Figure 15 (c) when the mole fraction of the rare earth element in the source solution is 0 at%, it was confirmed that only the soft magnetic properties of fcc-Fe.
  • 16 and 17 are graphs showing the effect of the mole fraction of the rare earth elements contained in the source solution on the structure of the hybrid magnetic fiber according to Example 1 of the present invention.
  • the hybrid magnetic fiber according to Example 2 wherein the mole fraction of rare earth element (Sm) in the source solution is controlled to be 10.56 at%, 0 at%, 9.91 at%, and 4.80 at% X-ray diffraction analysis by measuring the relative intensity (au) according to 2 ⁇ (degree) for each, and these are respectively (a) of Figure 16, (b) of Figure 16, (a) of Figure 17, and Figure 17 It is shown in (b).
  • Sm rare earth element
  • FIG. 18 is a graph showing the characteristics of a hybrid magnetic fiber according to a comparative example of the present invention in which no magnetic exchange coupling effect occurs.
  • an Applied field (kOe) of a hybrid magnetic fiber according to a comparative example of the present invention in which Sm 2 Co 17 light magnetic material and fcc-Co soft magnetic material are simply mixed in a volume ratio of 50 vol%: 50 vol%. Magnetization (emu / g) was measured according to) and the magnetic hysteresis curve was shown.
  • the hybrid magnetic fiber according to Example 1 in which the volume fraction of the Sm 2 Co 17 magnetic crystal and the fcc-Co magnetic boundary layer was controlled to 50 vol%: 50 vol%, was considered to exhibit a kink phenomenon. , It was confirmed that the effect of the auto-exchange coupling did not occur.
  • Example 19 is a graph showing the effect of the volume fraction of the magnetic boundary layer on the magnetic properties of the hybrid magnetic fiber according to Example 1 of the present invention.
  • the kink phenomenon does not appear in the magnetic hysteresis curve, the magnetic exchange coupling effect was confirmed to occur.
  • the hybrid magnetic fiber according to Example 1 exhibits the highest maximum magnetic energy ((BH) max ) value when the volume fraction of the fcc-Co magnetic boundary layer is 1 vol%. I could confirm it. Accordingly, when the volume fraction of the fcc-Co magnetic boundary layer is 1 vol%, it was found that the effect of the magnetic exchange coupling between the Sm 2 Co 17 magnetic crystal and the fcc-Co magnetic boundary layer is maximized.
  • (BH) max maximum magnetic energy
  • the size of the soft magnetic material should be smaller than twice the domain-wall width of the magnetic domain boundary.
  • the theoretical size of the fcc-Co magnetic boundary layer which is necessary to exhibit the effect of the magnetic exchange coupling between the Sm 2 Co 17 magnetic crystal and the fcc-Co magnetic boundary layer, is about 20.0 nm, which is less than about 5 at% when calculated by volume fraction. It can be seen that it is substantially in agreement with the experimental data of the invention.
  • Example 20 is a graph showing the effect of the volume fraction of the magnetic crystals on the residual magnetization value of the hybrid magnetic fiber according to Example 1 of the present invention.
  • the residual magnetization value (Remanence, M r (emu / g)) of the hybrid magnetic fiber according to Example 1, in which the volume fraction of the Sm 2 Co 17 magnetic crystal is controlled, is shown.
  • the volume fraction of the Sm 2 Co 17 magnetic crystal was 90 vol% or more, it was confirmed that the residual magnetization value was higher than that of the Sm 2 Co 17 single phase.
  • 21 is a graph showing the effect of the volume fraction of the magnetic crystal on the maximum magnetic energy value of the hybrid magnetic fiber according to Example 1 of the present invention.
  • the maximum magnetic energy value (Energy product, (BH) max (MGOe)) of the hybrid magnetic fiber according to Example 1, in which the volume fraction of the Sm 2 Co 17 magnetic crystal is controlled, is shown.
  • the maximum magnetic energy value was found to be the highest as 7.577 MGOe.
  • the hybrid magnetic fiber according to Example 1 when the volume fraction of the fcc-Co magnetic boundary layer is greater than 0 vol% less than 3 vol%, Sm 2 Co 17 magnetic crystals and fcc- It can be seen that the magnetic exchange coupling effect easily occurs between the Co magnetic boundary layers.
  • 22 and 23 are graphs showing modification of the Recoil curve of the hybrid magnetic fibers according to Example 1 of the present invention, in which the volume fractions of the magnetic crystals and the magnetic crystal layers are different.
  • Example 24 is a graph showing Recoil susceptibility values of hybrid magnetic fibers according to Example 1 of the present invention, in which the volume fractions of the magnetic boundary layers are different from each other.
  • dM / dH emu / (g. Oe) was measured to indicate the value of Recoil susceptibility.
  • one peak means that a magnetic exchange coupling effect occurs between the Sm 2 Co 17 magnetic crystal and the fcc-Co magnetic crystal layer, and the two peaks indicate the Sm 2 Co 17 magnetic crystal and fcc- It means that the magnetic exchange coupling effect does not appear between the Co magnetic crystal layers.
  • 25 to 27 is a graph comparing the characteristics of the heat treatment in the process of producing a hybrid magnetic fiber according to Example 1 of the present invention.
  • Relative intensity (au) according to 2theta (deg.) was measured to show an X-ray diffraction pattern.
  • Hybrid magnetic fibers heat treated at temperatures of 400 ° C., 500 ° C., 600 ° C., and 700 ° C. are shown in FIG. 25
  • hybrid magnetic fibers heat treated at temperatures of 700 ° C., 750 ° C., and 800 ° C. are shown in FIG. 26.
  • FIG. 27 is an enlarged graph of part A of FIG. 26.
  • the Sm 2 O 3 rare earth oxide is heat-treated at 25 ° C. to 1000 ° C. at a temperature increase rate of 10 ° C./mim in a hydrogen atmosphere, and then the weight loss (%) of the heat treated rare earth oxide is determined. Measured and shown. As can be seen from FIG. 28, in the case of the rare earth oxide, even when heat-treated at a temperature of 1000 ° C., there was almost no mass loss, and it was confirmed that the reduction was not easy.
  • 29 to 31 are photographs and graphs comparing the diameters of the hybrid magnetic fibers according to Examples 1 and 3 of the present invention.
  • FIG. 29A a SEM image of the hybrid magnetic fiber according to Example 3 is shown in FIG. 29A, and the diameter of the hybrid magnetic fiber is measured and illustrated in FIG. 29B.
  • the hybrid magnetic fiber according to Example 3 had a diameter of 250 nm or less and had a chain structure.
  • FIGS. 30A and 31A SEM images of the hybrid magnetic fibers according to Example 1 having a diameter of about 500 nm and a diameter of about 1000 nm are shown in FIGS. 30A and 31A, respectively.
  • the diameters of the hybrid magnetic fibers were measured and shown in FIGS. 30B and 31B.
  • the hybrid magnetic fiber according to Example 1 having a diameter of about 500 nm and a diameter of about 1000 nm has a magnetic crystal-magnetic boundary layer structure.
  • Hybrid magnetic fiber according to an embodiment of the present invention can be utilized in various industrial fields, such as permanent magnets, electric motors, micro relays, sensors.

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PCT/KR2019/001363 2018-07-03 2019-01-31 하이브리드 자성 섬유 및 그 제조방법 Ceased WO2020009303A1 (ko)

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