WO2020111386A1 - Fil magnétique de nitrure de fer et sa méthode de fabrication - Google Patents

Fil magnétique de nitrure de fer et sa méthode de fabrication Download PDF

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WO2020111386A1
WO2020111386A1 PCT/KR2019/001375 KR2019001375W WO2020111386A1 WO 2020111386 A1 WO2020111386 A1 WO 2020111386A1 KR 2019001375 W KR2019001375 W KR 2019001375W WO 2020111386 A1 WO2020111386 A1 WO 2020111386A1
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magnetic wire
preliminary
manufacturing
temperature
magnetic
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PCT/KR2019/001375
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English (en)
Korean (ko)
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김종렬
좌용호
강민규
이지민
황태연
이규태
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한양대학교 에리카산학협력단
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Publication of WO2020111386A1 publication Critical patent/WO2020111386A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0637—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with metals not specified in groups C01B21/0607 - C01B21/0635, other than aluminium, titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/10—One-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/42—(bi)pyramid-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the name relates to an iron nitride magnetic wire and a manufacturing method thereof, and relates to an iron nitride magnetic wire using a source solution containing Fe and a manufacturing method thereof.
  • Permanent magnets are a key material in industries that are widely used, from large equipment such as generators to small and medium equipment such as motors.
  • permanent magnets used in motors and generators are functional materials that play a key role in converting electrical energy into kinetic energy.
  • Recently, the production and demand of eco-friendly vehicles has rapidly increased due to the importance of replacing petroleum energy and low-carbon green growth, and the increase in the use of these motors has led to high efficiency, light weight, and miniaturization of motors, resulting in an explosive increase in the demand for rare earth permanent magnet materials. .
  • Rare earth-based permanent magnet materials show very high magnetic properties at room temperature, but have reached the theoretical maximum magnetic energy properties, and due to low thermal stability, a rapid decrease in properties occurs as the temperature increases.
  • heavy rare earth elements are added, but due to the unbalanced distribution of rare earth resources and the high price due to resource atomization, the high maximum magnetic energy of reducing or reducing rare earth elements in existing rare earth magnets or containing new rare earth elements Research is being conducted to find permanent magnet materials with enemies.
  • a substrate for example, in the Republic of Korea Patent Publication No. 10-2017-0108468 (application number: 10-2016-0032417, applicant: Yonsei University Industry-University Cooperation Foundation), a substrate, and formed on the substrate, a Bi thin film layer and a Mn thin film layer laminated Disclosed is a non-rare permanent magnet with improved coercive force including a thin film laminate obtained by repeatedly laminating and heat-treating units at least twice or more and a method for manufacturing the same.
  • One technical problem to be solved by the present invention is to provide an iron nitride magnetic wire with improved saturation magnetization value and a method for manufacturing the same.
  • Another technical problem to be solved by the present invention is to provide an iron nitride magnetic wire with improved coercive force and a method for manufacturing the same.
  • Another technical problem to be solved by the present invention is to provide an iron nitride magnetic wire capable of improving magnetic properties in a simple process 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 magnetic wire manufacturing method.
  • the method of manufacturing the magnetic wire is electrospinning a source solution containing Fe to form a first preliminary magnetic wire, and heat-treating the first preliminary magnetic wire at a first temperature to generate Fe oxide.
  • Forming a second preliminary magnetic wire, heat-treating the second preliminary magnetic wire at a second temperature to form a third preliminary magnetic wire with reduced Fe oxide, and the third preliminary magnetic wire Heat-treating at a source gas atmosphere containing nitrogen and a third temperature to form a magnetic wire in which nitrogen is penetrated into the third preliminary magnetic wire,
  • It may include controlling the saturation magnetization value of the magnetic wire by controlling at least one of the first to third temperatures.
  • the first temperature may include more than 600 °C less than 800 °C.
  • a nitrogen atom (atom) decomposed from the source gas is penetrated into the magnetic wire, and the infiltrated nitrogen atom includes bonding with Fe included in the magnetic wire. can do.
  • the saturation magnetization value may be controlled by controlling the flow rate of the source gas provided in the forming of the magnetic wire.
  • the source gas may include that provided at a flow rate of 1.5 L/min or more.
  • the forming of the second preliminary magnetic wire may include performing in one of an atmosphere or an oxygen (O 2 ) atmosphere.
  • the second temperature and the third temperature may include lower than the first temperature.
  • the source gas may include ammonia (NH 3 ).
  • the first temperature may include that the grain size of the magnetic wire increases.
  • the second preliminary magnetic wire may include Fe 2 O 3
  • the third preliminary magnetic wire may include ⁇ -Fe
  • the magnetic wire may include Fe 16 N 2 .
  • the present invention provides a magnetic wire.
  • the magnetic wire includes iron (Fe) and iron nitride (Fe x N y ), but the content of the iron nitride may be higher than the content of the iron. (x,y>0)
  • the iron nitride (Fe x N y ) may include more than 88.7wt%.
  • x may include 16 and y may include 2.
  • a method of manufacturing a magnetic wire comprises: electrospinning a source solution containing Fe to form a first preliminary magnetic wire, and heat-treating the first preliminary magnetic wire at a first temperature to Fe oxide.
  • Forming a second preliminary magnetic wire comprising, heat-treating the second preliminary magnetic wire at a second temperature to form a third preliminary magnetic wire with reduced Fe oxide, and the third preliminary magnetic wire.
  • it may include controlling the saturation magnetization value.
  • the magnetic wire manufacturing method according to the embodiment is a simple method for controlling the temperature of the heat treatment step, and increases the content of the iron nitride (Fe 16 N 2 ) contained in the magnetic wire, thereby improving the saturation magnetization value. I can do it.
  • the magnetic wire according to the embodiment may have a wire shape. In the case of the wire form, as it has a high aspect ratio, it can exhibit a shape magnetic anisotropy effect. Such a shape magnetic anisotropy effect can lead to an improvement in the coercive force.
  • iron nitride (Fe 16 N 2 ) wire having a saturation magnetization value of 176 emu/g or more and a coercive force of 1215 Oe or more, and a method of manufacturing the same can be provided.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a magnetic wire according to an embodiment of the present invention.
  • FIG. 2 is a view showing a magnetic wire manufacturing process according to an embodiment of the present invention.
  • FIG. 3 is a view showing equipment used in the manufacture of a magnetic wire according to an embodiment of the present invention.
  • FIG. 4 is a view showing a nitrogen penetration phenomenon in a method of manufacturing a magnetic wire according to an embodiment of the present invention.
  • FIG. 5 is a view for explaining the coercive force of the magnetic wire according to an embodiment of the present invention.
  • FIG. 6 is a photograph of the first preliminary magnetic wire formed during the manufacturing process of the magnetic wire according to the first embodiment of the present invention.
  • FIG 7 and 8 are photographs of the first preliminary magnetic wire formed during the manufacturing process of the magnetic wire according to Comparative Example 1 and Comparative Example 2 of the present invention.
  • Example 9 is a photograph of the first preliminary magnetic wire formed during the manufacturing process of the magnetic wire according to Example 2 of the present invention.
  • 10 to 12 are photographs of a second preliminary magnetic wire, a third preliminary magnetic wire, and a magnetic wire sequentially formed during the manufacturing process of the magnetic wire according to the first embodiment of the present invention.
  • FIG. 13 to 15 are photographs of a second preliminary magnetic wire, a third preliminary magnetic wire, and a magnetic wire sequentially formed during the manufacturing process of the magnetic wire according to the second embodiment of the present invention.
  • 16 to 18 are photographs of a second preliminary magnetic wire, a third preliminary magnetic wire, and a magnetic wire sequentially formed during the manufacturing process of the magnetic wire according to Example 3 of the present invention.
  • 19 to 21 are photographs of a second preliminary magnetic wire, a third preliminary magnetic wire, and a magnetic wire sequentially formed during the manufacturing process of the magnetic wire according to Example 4 of the present invention.
  • Example 24 is a graph analyzing the components of each of the second preliminary magnetic wire, the third preliminary magnetic wire, and the magnetic wire sequentially formed during the manufacturing process of the magnetic wire according to Example 2 of the present invention.
  • 25 and 26 are graphs showing a characteristic change according to the heat treatment temperature of the first preliminary magnetic wire during the manufacturing process of the magnetic wire according to the embodiment of the present invention.
  • FIG. 27 is a graph analyzing the components of the magnetic wires according to Examples 1 to 4 of the present invention.
  • 29 to 32 are graphs showing characteristics of the second preliminary magnetic wire formed during the manufacturing process of the magnetic wires according to Examples 1 to 4 of the present invention.
  • 35 is a graph showing a configuration change according to a flow rate of ammonia gas in a manufacturing process of a magnetic wire according to an embodiment of the present invention.
  • Example 36 is a graph showing magnetic properties of a magnetic wire according to Example 6 of the present invention.
  • a component when referred to as being on another component, it means that it may be formed directly on another component, or a third component may be interposed between them.
  • a third component may be interposed between them.
  • the thickness of the films and regions are exaggerated for effective description of the technical content.
  • 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 component. Therefore, what is referred to as the first component in one embodiment may be referred to as the second component in another embodiment.
  • first component in one embodiment may be referred to as the second component in another embodiment.
  • second component in another embodiment.
  • Each embodiment described and illustrated herein also includes its complementary embodiment.
  • 'and/or' is used to mean including at least one of the components listed before and after.
  • FIG. 1 is a flow chart illustrating a method of manufacturing a magnetic wire according to an embodiment of the present invention
  • Figure 2 is a view showing a magnetic wire manufacturing process according to an embodiment of the present invention
  • Figure 3 is according to an embodiment of the present invention
  • FIG. 4 is a diagram showing equipment used in the manufacture of a magnetic wire
  • FIG. 4 is a diagram showing a nitrogen infiltration phenomenon in a method of manufacturing a magnetic wire according to an embodiment of the present invention
  • FIG. 5 is a magnetic wire according to an embodiment It is a view for explaining the coercive force of.
  • a source solution containing Fe may be prepared.
  • the source solution may include iron nitrate hexahydrate (Iron(III) nitrate nonahydrate, Fe(NO 3 ) 3 9H 2 O).
  • the source solution may further include a viscous source.
  • 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 can contain.
  • the viscous source can provide viscosity to the source solution to control the diameter of the magnetic wire to be described later.
  • the source solution is electrospinned, so that the first preliminary magnetic wire 110 may be formed (S110).
  • the first preliminary magnetic wire 110 may be in a state in which a Fe salt and a polymer (eg, PVP) are mixed.
  • the source solution may be injected into a syringe (10), and the source solution may be radiated using a syringe pump (20).
  • the tip 30 of the syringe has a diameter of 0.05 to 2 mm
  • the syringe tip 30 and the collector 40 to which the preliminary hybrid magnetic fibers are collected are spaced 15 cm apart
  • the syringe pump 20 Can release the source solution at a rate of 0.2 to 0.8 mL/h.
  • the voltage applied for electric radiation may be 16-20 kV.
  • the first preliminary magnetic wire may be formed through the above-described process.
  • the first preliminary magnetic wire 110 may be heat treated at a first temperature. Accordingly, the second preliminary magnetic wire 120 may be formed (S120). In addition, the first preliminary magnetic wire 110 may be heat-treated in one of an atmosphere (air) atmosphere or an oxygen (O 2 ) atmosphere. When the first preliminary magnetic wire 110 is heat-treated at the first temperature, polymers and organic substances included in the first preliminary magnetic wire 110 are removed, and Fe may be oxidized. Accordingly, the second preliminary magnetic wire 120 may include Fe oxide. For example, the second preliminary magnetic wire 120 may include Fe 2 O 3 .
  • the first temperature may be controlled.
  • the first temperature may be different depending on the heat treatment atmosphere of the first preliminary magnetic wire 110. Specifically, when the first preliminary magnetic wire 110 is heat-treated in an oxygen (O 2 ) atmosphere, the first temperature may be controlled to 600°C. In this case, the content of iron nitride (Fe 16 N 2 ) in the magnetic wire to be described later increases, so that the saturation magnetization value of the magnetic wire can be improved. More detailed description will be given later.
  • the first temperature when the first preliminary magnetic wire 110 is heat-treated in an air atmosphere, the first temperature may be controlled to be greater than 600°C and less than 800°C.
  • the content of iron nitride (Fe 16 N 2 ) in the magnetic wire to be described later increases, so that the saturation magnetization value of the magnetic wire can be improved.
  • the first temperature when the first temperature is controlled to 600° C. or less, the removal of organic substances and polymers in the first preliminary magnetic wire 110 is not easily performed, and thus the formation of a magnetic wire described later may not be easy.
  • the first temperature when the first temperature is controlled to 800° C. or higher, a grain size of the magnetic wire to be described later increases, which may cause a problem of forming in a particle shape rather than a wire shape. That is, the magnetic wire to be described later may increase the size of the crystal grains as the first temperature increases, and when the size of the crystal grains exceeds a predetermined size, may exhibit a particle shape. Accordingly, the first temperature may be controlled so that the grain size of the magnetic wire does not exceed a predetermined size.
  • the second preliminary magnetic wire 120 may be heat treated at a second temperature.
  • the second preliminary magnetic wire 120 may be heat treated in a hydrogen (H 2 ) atmosphere. Accordingly, the Fe oxide included in the first preliminary magnetic wire 110 is reduced, and a third preliminary magnetic wire 130 may be formed (S130 ).
  • the third preliminary magnetic wire 130 may include ⁇ -Fe.
  • the second temperature may be controlled.
  • the second temperature may be lower than the first temperature.
  • the second temperature can be controlled to 290 °C.
  • the content of iron nitride (Fe 16 N 2 ) in the magnetic wire to be described later increases, so that the saturation magnetization value of the magnetic wire can be improved.
  • the third preliminary magnetic wire 130 may be heat treated at a third temperature in a source gas atmosphere containing nitrogen. Accordingly, the magnetic wire 200 according to the embodiment may be formed (S140). According to one embodiment, the source gas may include ammonia (NH 3 ).
  • the magnetic wire 200 may include iron nitride (Fe x N y ) in which a nitrogen atom and Fe are bonded.
  • the magnetic wire may include the iron nitride (Fe x N y ), and the iron (Fe) remaining unbound with nitrogen. (x,y>0)
  • the iron nitride (Fe x N y ) may be Fe 16 N 2 .
  • the saturation magnetization value of the magnetic wire may be improved.
  • the content of iron nitride (Fe 16 N 2 ) in the magnetic wire is the first temperature in the step of forming the second preliminary magnetic wire 120, and the third preliminary magnetic wire 130 is formed. It can be increased by controlling the second temperature in the step. That is, as a simple method of controlling the first temperature and the second temperature, the content of iron nitride (Fe 16 N 2 ) in the magnetic wire is increased, so that the saturation magnetization value of the magnetic wire 200 may be improved.
  • the flow rate of the source gas provided to the third preliminary magnetic wire 130 may be controlled.
  • the source gas may be provided at a flow rate of 1.5 L/min or more. Accordingly, the content of the iron nitride (Fe 16 N 2 ) included in the magnetic wire is increased, so that the saturation magnetization value can be improved.
  • the ammonia gas when the ammonia (NH 3 ) gas is provided to the third preliminary magnetic wire 130, due to the temperature and the catalytic effect of the Fe surface, the ammonia gas is a nitrogen atom, as shown in ⁇ Formula 1> below. It can be decomposed into hydrogen atoms. Then, the decomposed nitrogen atom and the hydrogen atom may be formed in a nitrogen molecular state as shown in ⁇ Formula 2> below.
  • the iron nitride (Fe 16 N 2 ) may be formed by combining nitrogen in the atomic state with Fe.
  • a nitrogen atom decomposed from ammonia (NH 3 ) gas a nitrogen molecule is formed over time, and in the case of a nitrogen molecule, it may not be combined with Fe. Accordingly, by increasing the flow rate of the source gas provided to the third preliminary magnetic wire 130 to increase the amount of nitrogen atoms that can be combined with Fe, the magnetic wire 200 includes the The content of iron nitride (Fe 16 N 2 ) can be increased.
  • the flow rate of the source gas exceeds a predetermined flow rate, the amount of nitrogen atoms bound to Fe is saturated, so that the content of the iron fine iron (Fe 16 N 2 ) included in the magnetic wire 200 is It can remain substantially the same.
  • the ammonia (NH 3 ) gas is provided at a flow rate of 1.5 L/min or higher, the content of the iron nitride (Fe 16 N 2 ) included in the magnetic wire 200 is increased to improve the saturation magnetization value. I can do it.
  • the third temperature may be controlled.
  • the third temperature may be lower than the first and second temperatures.
  • the third temperature can be controlled to 160 °C.
  • the content of iron nitride (Fe 16 N 2 ) in the magnetic wire 200 increases, so that the saturation magnetization value of the magnetic wire 200 may be improved.
  • the third preliminary magnetic wire forming step (S130), and the magnetic wire forming step (S140) may be performed in an in-situ process. In this case, formation of contaminants and oxide layers on the surface of the third preliminary magnetic wire can be suppressed. Accordingly, the magnetic wire can be easily formed.
  • iron nitride (Fe 16 N 2 ) nanoparticles were prepared by providing ammonia (NH 3 ) gas to an Fe powder, and in this process, an oxide film was formed on the surfaces of Fe particles to form nitrogen. A problem that penetration of the product is not easily generated may occur.
  • magnetic nanoparticles including iron nitride (Fe 16 N 2 ) as illustrated in FIG. 5, aggregation may occur between particles to reduce surface energy. Such agglutination may cause magnetostain coupling and intergranulae exchange coupling between particles, and may act as a major cause of reducing coercive force.
  • iron nitride (Fe 16 N 2) If the magnetic nanoparticles (particle) containing iron nitride (Fe 16 N 2) exhibits a high saturation magnetization due to inherent material properties, due to specific aggregation particles A problem that the coercive force is lowered may occur. In addition, in the process of manufacturing iron nitride (Fe 16 N 2 ) magnetic nanoparticles, the penetration of nitrogen is not easily generated, and a problem that iron nitride (Fe 16 N 2 ) is not easily formed may occur.
  • the source solution containing Fe is electrospun to form the first preliminary magnetic wire 110, and the first preliminary magnetic wire 110 is formed.
  • the step of forming the magnetic wire 200 may include, but may include controlling a saturation magnetization value by controlling at least one of the first to third temperatures.
  • the magnetic wire manufacturing method is a simple method of controlling the temperature of the heat treatment step, and increases the content of the iron nitride (Fe 16 N 2 ) contained in the magnetic wire 200 to increase the saturation magnetization.
  • the value can be improved.
  • the magnetic wire 200 according to the embodiment may have a wire shape.
  • the wire form as it has a high aspect ratio, it can exhibit a shape magnetic anisotropy effect. Such a shape magnetic anisotropy effect can lead to an improvement in the coercive force.
  • nitrogen penetration can be easily generated, so that the content of iron nitride (Fe 16 N 2 ) can be increased.
  • iron nitride (Fe 16 N 2 ) wire having a saturation magnetization value of 176 emu/g or more and a coercive force of 1215 Oe or more, and a method of manufacturing the same can be provided.
  • Iron(III) nitrate nonahydrate, Fe(NO 3 ) 3 9H 2 O), 1,300,000 molecular weight polyvinylpyrrolidone (PVP), and 6 ml of ethanol were added to 3 ml of deionized water.
  • the source solution was prepared by mixing. At this time, the concentration of PVP was prepared at 3.4 wt% compared to the source solution.
  • the prepared source solution is placed in a syringe for electrospinning, and the solution is continuously pushed at a rate of 0.4 mL/h using a syringe pump. At this time, the tip portion of the syringe and the collector where the emitted wire is collected are spaced at 15 cm intervals, and a high voltage of 18 kV is applied to radiate the source solution by a potential difference. Thus, a first preliminary magnetic wire was produced.
  • the first preliminary magnetic wire was collected in an alumina (Al 2 O 3 ) crucible and heat-treated at an air temperature of 600° C. for 1 hour. In this process, polymers and organic substances in the first preliminary magnetic wire were decomposed to produce a second preliminary magnetic wire.
  • alumina Al 2 O 3
  • the second preliminary magnetic wire was heat-treated at a temperature of 320° C. in a hydrogen (H 2 ) atmosphere. In this process, Fe oxide in the second preliminary magnetic wire was reduced to produce a third preliminary magnetic wire.
  • the third preliminary magnetic wire was heat-treated at a temperature of 160°C in an ammonia (NH 3 ) gas atmosphere.
  • NH 3 ammonia
  • nitrogen atoms decomposed from the ammonia gas penetrated into the third preliminary magnetic wire to form Fe 16 N 2 iron nitride.
  • a magnetic wire according to Example 1 including Fe 16 N 2 iron nitride and Fe was prepared.
  • Example 2 Prepared by the method of manufacturing the magnetic wire according to Example 1, the temperature of the heat treatment in the process of manufacturing the second preliminary magnetic wire was controlled to 700°C. Thus, a magnetic wire according to Example 2 was produced.
  • Example 3 Prepared by the manufacturing method of the magnetic wire according to Example 1, the temperature of the heat treatment in the process of manufacturing the second preliminary magnetic wire was controlled to 800°C. Thus, a magnetic wire according to Example 3 was produced.
  • Example 4 Prepared by the manufacturing method of the magnetic wire according to Example 1, the temperature of heat treatment in the process of manufacturing the second preliminary magnetic wire was controlled to 900°C. Thus, a magnetic wire according to Example 4 was produced.
  • Example 5 Prepared by the method of manufacturing the magnetic wire according to Example 1, the temperature of the heat treatment in the process of manufacturing the second preliminary magnetic wire was controlled to 700°C. In addition, the temperature to be heat-treated in the process of manufacturing the third preliminary magnetic wire was controlled to 305°C. Thus, a magnetic wire according to Example 5 was produced.
  • Example 6 Prepared by the method of manufacturing the magnetic wire according to Example 1, the temperature of the heat treatment in the process of manufacturing the second preliminary magnetic wire was controlled to 700°C. In addition, the temperature to be heat-treated in the process of manufacturing the third preliminary magnetic wire was controlled to 290°C. Thus, a magnetic wire according to Example 6 was produced.
  • the temperature of the heat treatment in the process of manufacturing the second preliminary magnetic wire was controlled to 700°C.
  • the temperature to be heat-treated in the process of manufacturing the third preliminary magnetic wire was controlled to 290°C.
  • the heat treatment temperature was controlled to 150°C.
  • the temperature of the heat treatment in the process of manufacturing the second preliminary magnetic wire was controlled to 700°C.
  • the temperature to be heat-treated in the process of manufacturing the third preliminary magnetic wire was controlled to 290°C.
  • the heat treatment temperature was controlled to 140°C.
  • Example 9 Prepared by the manufacturing method of the magnetic wire according to Example 1, the conditions of heat treatment in the process of manufacturing the second preliminary magnetic wire were controlled in an oxygen (O 2 ) atmosphere. Thus, a magnetic wire according to Example 9 was produced.
  • Example 10 Prepared by the manufacturing method of the magnetic wire according to Example 1, the conditions of heat treatment in the process of manufacturing the second preliminary magnetic wire were controlled in an oxygen (O 2 ) atmosphere, and the heat treatment temperature was controlled at 700°C. Thus, a magnetic wire according to Example 10 was produced.
  • the second preliminary magnetic wire was controlled in an oxygen (O 2 ) atmosphere, and the heat treatment temperature was controlled to 800° C. under conditions of heat treatment in the process of manufacturing.
  • O 2 oxygen
  • the heat treatment temperature was controlled to 800° C. under conditions of heat treatment in the process of manufacturing.
  • Example 12 Prepared by the manufacturing method of the magnetic wire according to Example 1, the conditions of heat treatment in the process of manufacturing the second preliminary magnetic wire were controlled in an oxygen (O 2 ) atmosphere, and the heat treatment temperature was controlled at 900°C. Thus, a magnetic wire according to Example 12 was produced.
  • the concentration of PVP in the process of preparing the source solution was controlled to be 2.1 wt% compared to the source solution.
  • citric acid at a concentration of 0.5 M was further added.
  • Example 1 3.4 wt% Air 600°C 320°C 160°C
  • Example 2 3.4 wt% Air 700°C 320°C 160°C
  • Example 3 3.4 wt% Air 800°C 320°C 160°C
  • Example 4 3.4 wt% Air 900°C 320°C 160°C
  • Example 5 3.4 wt% Air 700°C 305°C 160°C
  • Example 6 3.4 wt% Air 700°C 290°C 160°C
  • Example 7 3.4 wt% Air 700°C 290°C 150°C
  • Example 8 3.4 wt% Air 700°C 290°C 140°C
  • Example 9 3.4 wt% Oxygen (O 2 ) 600°C 320°C 160°C
  • Example 10 3.4 wt% Oxygen (O 2 ) 700°C 320°C 160°C
  • Example 11 3.4 wt%
  • FIG. 6 is a photograph of the first preliminary magnetic wire formed during the manufacturing process of the magnetic wire according to the first embodiment of the present invention.
  • Example 1 a magnetic wire according to Example 1 was prepared, but a first preliminary magnetic wire formed through electrospinning of the source solution during the manufacturing process of the magnetic wire was photographed by SEM (Scanning Electron Microscope). As can be seen from FIG. 6, it was confirmed that the first preliminary magnetic wire has a wire shape.
  • FIG 7 and 8 are photographs of the first preliminary magnetic wire formed during the manufacturing process of the magnetic wire according to Comparative Example 1 and Comparative Example 2 of the present invention.
  • Example 9 is a photograph of the first preliminary magnetic wire formed during the manufacturing process of the magnetic wire according to Example 2 of the present invention.
  • the magnetic wire according to Example 2 was prepared, but the first preliminary magnetic wire formed through electrospinning of the source solution during the manufacturing process of the magnetic wire was SEM photographed.
  • 9(a) and 9(b) show photographs of different magnifications.
  • the first preliminary magnetic wire formed during the manufacturing process of the magnetic wire according to Example 2 was formed in a wire shape having a constant thickness without forming a bead.
  • 10 to 12 are photographs of a second preliminary magnetic wire, a third preliminary magnetic wire, and a magnetic wire sequentially formed during the manufacturing process of the magnetic wire according to the first embodiment of the present invention.
  • the second preliminary magnetic wire, the third preliminary magnetic wire, and the magnetic wire are all formed in the form of a wire.
  • the prepared magnetic wire had a diameter of 100 to 300 nm, and a length of 10 ⁇ m or more.
  • FIG. 13 to 15 are photographs of a second preliminary magnetic wire, a third preliminary magnetic wire, and a magnetic wire sequentially formed during the manufacturing process of the magnetic wire according to the second embodiment of the present invention.
  • the second preliminary magnetic wire, the third preliminary magnetic wire, and the magnetic wire are all formed in the form of wires.
  • the prepared magnetic wire had a diameter of 100 to 300 nm, and a length of 10 ⁇ m or more.
  • 16 to 18 are photographs of a second preliminary magnetic wire, a third preliminary magnetic wire, and a magnetic wire sequentially formed during the manufacturing process of the magnetic wire according to Example 3 of the present invention.
  • the second preliminary magnetic wire, the third preliminary magnetic wire, and the magnetic wire are all formed in the form of a wire.
  • the prepared magnetic wire had a diameter of 100 to 300 nm, and a length of 10 ⁇ m or more.
  • 19 to 21 are photographs of a second preliminary magnetic wire, a third preliminary magnetic wire, and a magnetic wire sequentially formed during the manufacturing process of the magnetic wire according to Example 4 of the present invention.
  • the second preliminary magnetic wire, the third preliminary magnetic wire, and the magnetic wire formed during the process of manufacturing the magnetic wire according to Example 4 are all exhibiting coarsening of particles. I could confirm. In addition, it was confirmed that the magnetic wire according to Example 4 was formed closer to the particle shape than the wire shape.
  • Crystallite sizes of the magnetic wires according to Examples 1 to 4 identified through FIGS. 10 to 21 are summarized through Table 2 below.
  • the first pre-heating temperature of the magnetic wire is 600°C, 700°C, 800°C, and As it was increased to 900°C, it was confirmed that the particle size of the magnetic wire finally formed increased. In addition, when the heat treatment temperature of the first preliminary magnetic wire exceeds 800°C, it was confirmed that the final formed magnetic wire is formed closer to the particle shape than the wire shape.
  • Example 24 is a graph analyzing the components of each of the second preliminary magnetic wire, the third preliminary magnetic wire, and the magnetic wire sequentially formed during the manufacturing process of the magnetic wire according to Example 2 of the present invention.
  • the second preliminary magnetic wire contains Fe 2 O 3, that is, Fe oxide.
  • Fe 3 O 3 contained reduced Fe in the case of the third preliminary magnetic wire.
  • FIG. 24(c) it was confirmed that in the case of the magnetic wire, Fe 16 N 2 containing nitrogen (N) atoms bonded to Fe was included. However, in the case of the magnetic wire, it was confirmed that not only Fe 16 N 2 but also Fe was included.
  • 25 and 26 are graphs showing a characteristic change according to the heat treatment temperature of the first preliminary magnetic wire during the manufacturing process of the magnetic wire according to the embodiment of the present invention.
  • a magnetic wire is manufactured according to a manufacturing process of a magnetic wire according to an embodiment of the present invention, but the heating temperature of the first preliminary magnetic wire is 0°C to 1000°C at a heating rate of 10°C/min.
  • the magnetic wire thus formed was subjected to TG-DTA (Thermogravimetry-Differential Thermal Analysis) and the results are shown.
  • the concentration of PVP in the source solution used in the manufacturing process is 3.4 wt%.
  • the first preliminary magnetic wire by changing the heat treatment temperature to 0 ⁇ 1000 °C magnetic wire is formed Only 3 times, it was confirmed that a significant change in weight occurred.
  • the first weight change occurs at 100°C, which is believed to occur as moisture in the first pre-magnetic wire evaporates.
  • the second weight change occurs at a portion of 200°C to 250°C, which is judged to occur as organic matter and PVP in the first preliminary magnetic wire are removed.
  • the third weight change occurs at 300°C to 400°C, which is thought to be caused by the removal of residual PVP in the first preliminary magnetic wire and decomposition of NO 3 in the third preliminary magnetic wire.
  • FIG. 27 is a graph analyzing the components of the magnetic wires according to Examples 1 to 4 of the present invention.
  • the magnetic wires according to Examples 1 to 4 were composed of Fe 16 N 2 and Fe.
  • the magnetic wires according to Examples 9 to 12 were also confirmed to be composed of Fe 16 N 2 and Fe. Further, it was confirmed that the magnetic wire according to the ninth embodiment, in which the first preliminary magnetic wire was heat-treated at a temperature of 600° C., had the highest Fe 16 N 2 content.
  • 29 to 32 are graphs showing characteristics of the second preliminary magnetic wire formed during the manufacturing process of the magnetic wires according to Examples 1 to 4 of the present invention.
  • the intensity (CPS) according to 2-Theta (deg.) is measured, and 2 The crystallite size of the preliminary magnetic wire was calculated.
  • the grain size was calculated by using Scherrer's equation to broaden the peaks shown in each graph.
  • the second preliminary magnetic wires formed during the manufacturing process of the magnetic wires according to Examples 1 to 4 were 180 ⁇ , 290 ⁇ , 314 ⁇ , and 329 ⁇ in diameter, respectively. .
  • Example 33 2-Theta (deg. for each of the magnetic wires according to Example 2 (reduction temperature 320°C), Example 5 (reduction temperature 305°C), and Example 6 (reduction temperature 290°C). ) Intensity (arb.units) according to the measured components were analyzed. As can be seen in FIG. 33, it was confirmed that the magnetic wire according to Example 6, in which the second preliminary magnetic wire was reduced at a temperature of 290° C., had the highest Fe 16 N 2 content of 88.7 wt%.
  • Example 6 2-Theta (deg. for each of the magnetic wires according to Example 6 (nitride temperature 160°C), Example 7 (nitride temperature 150°C), and Example 8 (nitride temperature 140°C). ) Intensity (arb.units) according to the measured components were analyzed. As can be seen in FIG. 34, it was confirmed that the magnetic wire according to Example 6, in which the third preliminary magnetic wire was nitrided at a temperature of 160° C., had the highest Fe 16 N 2 content of 86.2 wt%.
  • 35 is a graph showing a configuration change according to a flow rate of ammonia gas in a manufacturing process of a magnetic wire according to an embodiment of the present invention.
  • a magnetic wire is manufactured according to the manufacturing process of the magnetic wire according to Example 2, but the flow rate of ammonia gas provided in the heat treatment process of the third preliminary wire is 0.5 L/min, 1.0 L/min, And 1.5 L/min, and analyzed the components of the magnetic wire prepared according to each.
  • the flow rate of ammonia gas provided in the heat treatment process of the third preliminary wire is 0.5 L/min, 1.0 L/min, And 1.5 L/min, and analyzed the components of the magnetic wire prepared according to each.
  • the flow rate of ammonia gas provided in the heat treatment process of the third preliminary wire is 0.5 L/min, 1.0 L/min, And 1.5 L/min
  • nitrogen atoms decomposed from ammonia gas are formed of nitrogen molecules over time, and nitrogen molecules cannot be penetrated into the third preliminary magnetic wire, so that Fe 16 N 2 iron nitride cannot be formed. Is judged. That is, it can be seen that the penetration into the nitrogen atom is the third spare magnetic wire Fe 16 N 2 iron nitride is formed, 1.5 L / min flow rate at least ammonia gas has to be provided, the iron nitride Fe 16 N 2 that is easily formed.
  • Example 36 is a graph showing magnetic properties of a magnetic wire according to Example 6 of the present invention.
  • the magnetic properties of the magnetic wire according to Example 6 were measured by measuring the intensity (arb.units) according to Applied Filed(Oe).
  • the magnetic properties measured through FIG. 36 are summarized in ⁇ Table 5> below.
  • the magnetic wire according to Example 6 exhibited a high saturation magnetization value of 176 emu/g or higher and a high coercive force of 1215 Oe or higher.
  • the iron nitride magnetic nanowire according to an embodiment of the present invention can be used in various industrial fields such as permanent magnets, electric motors, sensors, and automobiles.

Abstract

L'invention concerne une méthode de fabrication d'un fil magnétique. La méthode de fabrication d'un fil magnétique peut comprendre les étapes consistant à : former un premier fil magnétique préliminaire par électrofilage d'une solution source comprenant du Fe ; former un second fil magnétique préliminaire comprenant de l'oxyde de Fe par réalisation d'un traitement thermique sur le premier fil magnétique préliminaire à une première température ; réaliser un traitement thermique sur le second fil magnétique préliminaire à une seconde température, formant ainsi un troisième fil magnétique préliminaire dans lequel l'oxyde de Fe est réduit ; et réaliser, à une troisième température, un traitement thermique sur le troisième fil magnétique préliminaire dans une atmosphère de gaz source comprenant de l'azote, formant ainsi un fil magnétique dans lequel de l'azote pénètre dans le troisième fil magnétique préliminaire.
PCT/KR2019/001375 2018-11-30 2019-01-31 Fil magnétique de nitrure de fer et sa méthode de fabrication WO2020111386A1 (fr)

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KR20060043263A (ko) * 2004-03-17 2006-05-15 도와 마이닝 가부시끼가이샤 질화철 자성 분말 및 이의 제조방법
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