US20230099171A1 - L10 type iron-nickel ordered alloy and method of manufacturing l10 type iron-nickel ordered alloy - Google Patents

L10 type iron-nickel ordered alloy and method of manufacturing l10 type iron-nickel ordered alloy Download PDF

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US20230099171A1
US20230099171A1 US17/950,431 US202217950431A US2023099171A1 US 20230099171 A1 US20230099171 A1 US 20230099171A1 US 202217950431 A US202217950431 A US 202217950431A US 2023099171 A1 US2023099171 A1 US 2023099171A1
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feni
sulfur
nitriding
alloy
type
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Hiroaki Kura
Takahiro NISHIO
Eiji Watanabe
Yoshiaki Hayashi
Takayuki Yamamoto
Hisashi MAEHARA
Takanori Matsuno
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Nichia Corp
Denso Corp
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Nichia Corp
Denso Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24—Nitriding
    • C23C8/26—Nitriding of ferrous surfaces

Definitions

  • the present disclosure relates to an L1 0 type iron-nickel (FeNi) ordered alloy (hereinafter, also referred to as FeNi superlattice) having an L1 0 type ordered structure and a method of manufacturing an L1 0 type FeNi ordered alloy.
  • FeNi iron-nickel
  • FeNi superlattices are expected as magnet materials having high heat resistance and magnetic device materials such as magnetic recording materials.
  • an L1 0 type FeNi ordered alloy has an L1 0 type ordered structure and contains sulfur.
  • a manufacturing method of an L1 0 type FeNi ordered alloy includes performing a nitriding treatment to an FeNi alloy containing sulfur to obtain a nitride containing Fe and Ni.
  • FIG. 1 is a schematic diagram showing a lattice structure of an L1 0 type FeNi ordered structure
  • FIG. 2 is a schematic diagram showing a lattice structure of FeNiN
  • FIG. 3 is a flowchart showing a synthesis process of an FeNi superlattice according to a first embodiment
  • FIG. 4 is a flow chart showing a synthesis process of an FeNi superlattice according to a second embodiment
  • FIG. 5 is a diagram showing differences in FeNi superlattice manufacturing conditions, FeNiN formation rate, ammonia efficiency, and the like for each of Examples and Comparative Examples;
  • FIG. 6 is a diagram showing measurement results of powder X-ray diffraction (XRD) patterns of Comparative Example 2 and Example 3;
  • FIGS. 7 A to 7 D are diagrams showing results of cross-sectional TEM observation and composition image observation using a transmission electron microscope (TEM);
  • FIGS. 8 A to 8 D are diagrams showing results of cross-sectional TEM observation and composition image observation using the TEM
  • FIG. 9 is a diagram showing differences in FeNi superlattice manufacturing conditions, FeNiN formation rate, ammonia efficiency, and the like for each of Examples and Comparative Examples;
  • FIG. 10 is a diagram showing differences in FeNi superlattice manufacturing conditions, FeNiN formation rate, ammonia efficiency, and the like for each of Examples and Comparative Examples;
  • FIG. 11 is a diagram showing magnetic characteristics of FeNi superlattice magnetic powder obtained by using FeNiN of Comparative Example 2, Example 3 and Example 7;
  • FIG. 12 is a diagram showing X-ray absorption near edge spectra (XANES) for FeNi superlattice magnetic powder of each of Example 3 and Example 4.
  • XANES X-ray absorption near edge spectra
  • a high-quality FeNi superlattice can be manufactured using a nitriding and denitriding method in which an FeNi alloy is nitrided by a nitriding treatment to obtain a nitride, and then nitrogen is desorbed from the nitride by a denitriding treatment.
  • the present inventors repeatedly studied to improve the nitriding efficiency and confirmed that the nitriding efficiency is lowered because the nitride generated in the nitriding process is decomposed by heat.
  • an L1 0 type FeNi ordered alloy has an L1 0 type ordered structure and contains sulfur.
  • the L1 0 type FeNi ordered alloy contains sulfur, that is, when forming the L1 0 type FeNi ordered alloy using an FeNi alloy containing sulfur as a raw material, a high nitriding efficiency can be obtained.
  • a manufacturing method of an L1 0 type FeNi ordered alloy includes performing a nitriding treatment to an FeNi alloy containing sulfur to obtain a nitride containing Fe and Ni.
  • the term “process” is used not only as an independent process but also as a process included in other process as long as an intended purpose of the process is achieved even if it cannot be dearly distinguished from the other process.
  • the numerical range indicated by using “to” indicates a range including the numerical values before and after “to” as the minimum value and the maximum value, respectively.
  • the same or equivalent parts will be designated with the same reference numerals.
  • An L1 0 type FeNi ordered alloy of the present embodiment has an L1 0 ordered structure and contains sulfur.
  • the L1 0 type ordered alloy referred to here means that the regularity is 0.1 or more, and can be preferably 0.5 or more. Further, the upper limit of the regularity may be 1 or less.
  • the L1 0 type FeNi ordered alloy according to the present embodiment is suitably used as a magnetic powder and a magnetic material. Examples of the magnetic material include magnetic materials such as sintered magnets, bonded magnets, and magnetic recording materials.
  • the regularity S reg indicates the degree of the order in FeNi superlattice.
  • the L1 0 type ordered structure has a structure based on a face-centered cubic lattice, and has a lattice structure as shown in FIG.
  • an utmost upper layer in a stacking structure on a (001) plane of the face-centered cubic lattice is defined as site I
  • a middle layer disposed between the utmost upper layer and an utmost lower layer is defined as site II.
  • an existing ratio of metal A at site I is defined as x
  • an existing ratio of metal B at site I is defined as (1 ⁇ x).
  • the existing ratio of metal A and metal B at side I is expressed as A x B 1-x
  • an existing ratio of metal at site II is defined as x
  • an existing ratio of metal A at site II is defined as (1 ⁇ x).
  • the existing ratio of metal A and metal B at site II is expressed as A 1-x B x .
  • x satisfies a relationship of 0.5 ⁇ x ⁇ 1.
  • the estimation of the regularity S reg is performed using an estimation equation of the regularity S reg in the L1 0 type FeNi ordered alloy shown in the following equation 1.
  • I sup is an integrated intensity of a diffraction peak (superlattice diffraction peak) peculiar to the L1 0 type ordered alloy and found in an X-ray diffraction (XRD) pattern observed by an XRD method.
  • I fund is an integrated intensity of a diffraction peak (fundamental diffraction peak) appearing in both the FeNi alloy and the L1 0 type FeNi ordered alloy.
  • (I sup /I fund ) obs ” is a ratio of the integrated intensity of the superlattice diffraction peak and the integrated intensity of the fundamental diffraction peak in the X-ray diffraction pattern measured in each of Examples and Comparative Examples.
  • (I sup /I fund ) cal is a ratio of the integrated intensity of the superlattice diffraction peak of the FeNi ordered alloy having a regularity of 1 estimated from the Rietbelt simulation to the integrated intensity of the fundamental diffraction peak.
  • the regularity S reg is obtained by calculating a square root of these two ratios.
  • a general device such as a SmartLab manufactured by Rigaku Co., Ltd. can be used, but the regularity S reg can be estimated accurately by using Fe-k ⁇ rays as an X-ray.
  • the lower limit of the sulfur (S) content in the L1 0 type FeNi ordered alloy can be, for example, 0.01% by mass or more, preferably 0.03% by mass or more, and more preferably 0.1% by mass or more.
  • the upper limit of the S content in the L1 0 type FeNi ordered alloy can be, for example, 10% by mass or less, preferably 2.0% by mass or less, more preferably 1.5% by mass or less, more preferably 1.0% by mass or less, more preferably 0.75% by mass or less, and particularly preferably 0.53% by mass or less.
  • the S content can be measured by a method described in Examples below.
  • the oxidation number of sulfur (S) in the L1 0 type FeNi ordered alloy may include S 2 ⁇ or S 6+ or a mixed state of S 2 ⁇ and S 6+ .
  • the oxidation number of sulfur can be measured by XAFS measurement (that is, partial fluorescence yield measurement) described later.
  • the absorption peak appearing at 2482.0 ⁇ 2 eV in the XAFS measurement can be regarded as the peak due to S 6+
  • the absorption peak appearing at 2471.5 ⁇ 2 eV can be regarded as the peak due to S 2 ⁇ . Based on the presence of these absorption peaks, it can be determined that S 2 ⁇ and S 6+ are present.
  • the oxidation number of sulfur contained in the FeNi superlattice may be other than S 2 ⁇ and S 6+ as long as the effect of improving ammonia efficiency can be obtained.
  • the L 10 type FeNi ordered alloy may be composed of particles 100 having the L1 0 type ordered structure, as shown in FIGS. 7 and 8 described later.
  • S may be present throughout the particles, may be segregated inside the particles, or may be segregated on the particle surfaces.
  • the state of S can be measured by a method described in Examples below.
  • the lower limit of the average particle size can be, for example, 10 nm or more, preferably 50 nm or more, and more preferably 100 nm or more.
  • the upper limit of the average particle size can be, for example, 5000 nm or less, preferably 1000 nm or less, and more preferably 500 nm or less.
  • the average particle size can be measured from scanning electron microscope (SEM) images.
  • the L1 0 type FeNi ordered alloy may be composed of secondary particles in which primary particles are aggregated, and in that case, the lower limit of the average particle size of the primary particles may be, for example, 10 nm or more, preferably 30 nm, and more preferably 50 nm or more. Also, the upper limit of the average particle size of the primary particles can be, for example, 1000 nm or less, preferably 500 nm or less.
  • the average particle size of primary particles can be calculated by analyzing the XRD pattern by the Williamson-Hall method.
  • the ratio of the number of moles of Fe to the total number of moles of Fe and Ni in the L1 0 type FeNi ordered alloy may be 0.4 to 0.6, preferably 0.45 to 0.55, and more preferably 0.48 to 0.52.
  • the number of moles of Fe and Ni can be measured by inductively coupled plasma (ICP) emission spectroscopy, energy dispersive X-ray spectroscopy (EDS) using an electron microscope, or the like.
  • a manufacturing method of the L1 0 type FeNi ordered alloy according to the present embodiment includes performing a nitriding treatment to an FeNi alloy containing sulfur (S) to obtain a nitride containing Fe and Ni.
  • the FeNi alloy used in a nitriding process contains S, so that thermal decomposition of the FeNi nitrides generated in the nitriding process can be suppressed, which is thought to improve the nitriding efficiency.
  • the L1 0 type FeNi ordered alloy manufactured according to the present embodiment is suitably used as magnetic powder and magnetic material. Examples of the magnetic material include magnetic materials such as sintered magnets, bonded magnets, and magnetic recording materials.
  • an FeNi alloy containing S (hereinafter also referred to as FeNi—S) is nitrided to obtain a nitride containing Fe and Ni (hereinafter referred to as FeNi nitride).
  • the nitriding treatment is not particularly limited as long as FeNi nitride can be obtained from FeNi—S, but examples the nitriding treatment include gas nitriding with ammonia gas or nitrogen, plasma nitriding, and nitriding using metal amide. Specifically, the nitriding treatment is performed by heat-treating prefabricated FeNi—S under an ammonia gas flow.
  • the flow rate of the ammonia gas in the nitriding treatment can be 0.1 to 10 liters/min, preferably 0.5 to 5 liters/min, with respect to 1 g of FeNi—S.
  • the heat treatment temperature can be, for example, 300 to 500° C., preferably 310 to 475° C., and more preferably 330 to 450° C.
  • the heat treatment time can be, for example, 5 to 50 hours, preferably 10 to 20 hours.
  • the FeNi nitride obtained in the nitriding process may be an S-containing FeNi nitride (hereinafter also referred to as FeNi nitride-S).
  • the S-containing FeNi alloy used in the nitriding process may have a disordered structure.
  • the disordered structure referred to here may be one in which the arrangement of atoms is random without regularity, or the peak of the L1 0 type ordered structure is not observed when measured by X-ray diffraction.
  • the FeNi—S used in the nitriding process can be produced by adding a compound containing a predetermined amount of sulfur element (hereinafter also referred to as a sulfur compound) to an FeNi alloy produced by a known method, as necessary.
  • the FeNi—S can also be produced by mixing the FeNi alloy and the sulfur compound and then performing a heat treatment, or by reacting the FeNi alloy and the sulfur compound.
  • the FeNi—S can also be produced by partially sulfurizing the FeNi alloy with hydrogen sulfide gas or the like.
  • the sulfur compound should contain elemental sulfur, and examples of the sulfur compound include sulfur, organic sulfur compounds, metal sulfides such as iron sulfide and nickel sulfide, and sulfates such as ammonium sulfate, iron sulfate, and nickel sulfate.
  • FeNi—S used in the nitriding process may be synthesized during the nitriding process. Specifically, for example, FeNi nitride is formed by heat-treating the FeNi alloy under a mixed gas flow of ammonia gas and hydrogen sulfide so that synthesis and nitriding of FeNi nitride-S are performed in parallel (sulphonitriding).
  • the ratio of the number of moles of Fe to the total number of moles of Fe and Ni in FeNi—S used in the nitriding process may be 0.4 to 0.6, preferably 0.45 to 0.55, and more preferably 0.48 to 0.52.
  • the content of sulfur (S) in FeNi—S used in the nitriding process can be, for example, 0.01% by mass to 10% by mass, preferably 0.02% by mass to 2.0% by mass, more preferably 0.02% by mass to 1.5% by mass, more preferably 0.03% by mass to 1.0% by mass, and particularly preferably 0.05% by mass to 0.7% by mass.
  • S sulfur
  • the content of sulfur can be measured by the method described in Examples below.
  • FeNi nitride obtained in the nitriding process examples include FeNiN, Fe 2 Ni 2 N, and the like, and it is preferable that a ratio of FeNiN is large in order to obtain the L11 type FeNi ordered alloy.
  • FeNiN has a crystal structure as shown in FIG. 2 and can be identified from an XRD diffraction pattern.
  • the ratio of FeNi nitride contained after the nitriding process can be 90% by mass or more of the entire product.
  • the ratio of FeNiN in the FeNi nitride can be 50% by mass or more, and preferably 80% by mass or more.
  • the ratio of nitrides and the ratio of FeNiN after the nitriding process can be calculated by analyzing the XRD diffraction pattern by the reference intensity ratio (RIR) method.
  • RIR reference intensity ratio
  • the ratio of the number of moles of Fe to the total number of moles of Fe and Ni in the FeNi nitride obtained in the nitriding process may be 0.4 to 0.6, preferably 0.45 to 0.55, and more preferably 0.48 to 0.52.
  • the number of moles of Fe and Ni can be measured by inductively coupled plasma (ICP) emission spectroscopy, energy dispersive X-ray spectroscopy (EDS) using an electron microscope, or the like.
  • the FeNi nitride obtained in the nitriding process may contain sulfur (S).
  • the lower limit of the S content can be, for example, 0.01% by mass or more, preferably 0.03% by mass or more, and more preferably 0.05% by mass or more.
  • the upper limit of the S content in the L1 0 type FeNi ordered alloy can be, for example, 10% by mass or less, preferably 2.0% by mass or less, more preferably 1.5% by mass or less, more preferably 1.0% by mass or less, and particularly preferably 0.7% by mass or less.
  • the S content can be measured by a method described in Examples below.
  • the FeNi nitride obtained in the nitriding process contains S
  • the FeNi nitride may be composed of particles.
  • S may be present throughout the particles, or may be segregated inside the particles. Further, S may be segregated on the particle surface. The state of S can be measured by a method described in Examples below.
  • the lower limit of the average particle size can be, for example, 10 nm or more, preferably 50 nm or more, and more preferably 100 nm or more.
  • the upper limit of the average particle size can be, for example, 5000 nm or less, preferably 1000 nm or less, and more preferably 500 nm or less.
  • the average particle size can be measured from scanning electron microscope (SEM) images.
  • the FeNi nitride obtained in the nitriding process may be composed of secondary particles in which primary particles are aggregated, and in that case, the lower limit of the average particle size of the primary particles can be, for example, 10 nm or more, preferably 30 nm or more, and more preferably 50 nm or more. Also, the upper limit of the average particle size can be, for example, 1000 nm or less, preferably 500 nm or less.
  • the average particle size of primary particles can be calculated by analyzing the XRD pattern by the Williamson-Hall method.
  • the nitriding treatment is performed to FeNi—S. Accordingly, it is possible to obtain a high nitriding efficiency, as shown in Examples described later.
  • the nitriding efficiency in the nitriding process can be greater than 4.7 ⁇ 10 ⁇ 5 , preferably greater than 10 ⁇ 10 ⁇ 5 , and more preferably greater than 20 ⁇ 10 ⁇ 5 .
  • the term “nitriding efficiency” used in the present disclosure means the number obtained by dividing the amount (g) of FeNiN formed by the nitriding treatment by the nitrogen raw material (g) consumed in the nitriding treatment.
  • a nitriding efficiency in a case where ammonia is used as nitrogen source indicates the number obtained by dividing the formation amount (g) of FeNiN by the amount (g) of consumed ammonia, and is the ammonia amount required for synthesizing FeNiN.
  • a higher numerical value of ammonia efficiency means that FeNiN can be synthesized with a smaller amount of ammonia.
  • an L1 0 type FeNi ordered alloy containing S may be used as the FeNi alloy.
  • the L1 0 type FeNi ordered alloy containing S can be obtained by adding a predetermined amount of sulfur compound as necessary to the L1 0 type FeNi ordered alloy manufactured by a known method, in addition to the L1 0 type FeNi ordered alloy containing S described in the present embodiment.
  • the L1 0 type FeNi ordered alloy containing S can also be produced by mixing an L1 0 type FeNi ordered alloy and a sulfur compound and then performing a heat treatment, or by reacting an L1 0 type FeNi ordered alloy with a sulfur compound.
  • the L1 0 type FeNi ordered alloy containing S can also be produced partially sulfurizing an L1 0 type FeNi ordered alloy with hydrogen sulfide gas or the like.
  • the sulfur compound is as described above. In cases where FeNi—S having the L1 0 type ordered structure is used, an improvement in the regularity can be expected.
  • the FeNi nitride obtained in the above-described nitriding process is denitrided to obtain an L1 0 type FeNi ordered alloy.
  • a denitriding treatment can be performed by subjecting it to heat treatment in a hydrogen atmosphere.
  • the flow rate of hydrogen in the denitriding treatment can be 0.01 to 10 liters/min, preferably 0.1 to 5 liters/min, with respect to 1 g of FeNi nitride-S.
  • the heat treatment temperature can be, for example, 100 to 400° C., preferably 200 to 350° C.
  • the heat treatment time can be, for example, 1 to 24 hours, preferably 2 to 10 hours.
  • the L1 0 type FeNi ordered alloy obtained in the denitriding process may be an L1 0 type FeNi ordered alloy containing S.
  • a manufacturing method includes a reduction process of reducing an FeNi oxide containing S (hereinafter, also referred to as FeNi oxide-S) to obtain an FeNi—S.
  • FeNi oxide-S FeNi oxide containing S
  • a reduction method in the reduction process is not particularly limited, but for example, the FeNi—S can be obtained by heat-treating the FeNi oxide containing S in a reducing gas atmosphere.
  • the flow rate of the reducing gas can be 1 liter/min, preferably 0.5 to 10.0 liters/min, with respect to 8.5 g of the FeNi oxide-S.
  • the heat treatment temperature can be, for example, 300 to 700° C., and preferably 450 to 700° C.
  • the heat treatment time can be, for example, 1 to 10 hours, preferably 1.5 hours.
  • the reducing gas include hydrogen and carbon monoxide, and hydrogen is preferred from the viewpoint of reducing properties.
  • the ratio of the number of moles of Fe to the total number of moles of Fe and Ni in the FeNi oxide-S may be 0.4 to 0.6, preferably 0.45 to 0.55, and more preferably 0.48 to 0.52.
  • the FeNi oxide-S used in the reduction process may contain an Fe oxide, a Ni oxide, or an oxide containing Fe and Ni. Further, the Fe oxide, the Ni oxide, and the oxide containing Fe and Ni may each contain S.
  • the oxide containing Fe and Ni as used herein means containing Fe element and Ni element in one oxide particle.
  • the FeNi oxide-S used in the reduction process can be produced by adding a predetermined amount of sulfur compound as necessary to the FeNi oxide manufactured by the present embodiment or a known method.
  • the FeNi oxide-S can also be produced by mixing the FeNi oxide and the sulfur compound and then performing a heat treatment, or by reacting an FeNi oxide and a sulfur compound.
  • the FeNi oxide-S can also be produced by partially sulfurizing the FeNi oxide with hydrogen sulfide gas or the like.
  • the sulfur compound is as described above.
  • the FeNi oxide-S used in the reduction process may be synthesized during the reduction process. Specifically, for example, an FeNi oxide is heat-treated under a mixed gas flow of hydrogen gas and hydrogen sulfide so that synthesis and reduction of the FeNi oxide-S are performed in parallel.
  • the Fe oxide is not particularly limited.
  • the Fe oxide include FeO, Fe 2 O 3 , Fe 3 O 4 , and oxides obtained by oxidizing iron metal, iron hydroxide, iron carbonate, iron chloride, iron iodide, iron bromide, iron sulfate, iron nitrate, iron phosphate, and iron oxalate.
  • iron sulfate is preferable because it serves as a sulfur source for the Fe oxide containing S.
  • the Fe oxide containing S may be produced by the preparing method of the FeNi oxide-S described above.
  • the Ni oxide is not particularly limited.
  • the Ni oxide include NiO, and oxides obtained by oxidizing nickel metal, nickel hydroxide, nickel carbonate, nickel chloride, nickel iodide, nickel bromide, nickel sulfate, nickel nitrate, nickel phosphate, and nickel oxalate.
  • nickel sulfate is preferable because it serves as a sulfur source for the Ni oxide containing S.
  • the Ni oxide containing S may be produced by the preparing method of the FeNi oxide-S described above.
  • the oxide containing Fe and Ni can be produced by mixing a solution containing Fe and Ni with a precipitant to obtain a precipitate containing Fe and Ni (precipitation process), and heat-treating the precipitate to obtain the oxide containing Ni and Ni (oxidation process). According to this method, it is easy to control the average particle size and particle size distribution of the resulting oxide containing Fe and Ni, and the distribution of the Fe element and the Ni element in the oxide containing Fe and Ni tends to be uniform.
  • Fe raw material and Ni raw material are dissolved in a strongly acidic solution to prepare a solution containing Fe and Ni.
  • the Fe raw material and Ni raw material are not limited as long as they can be dissolved in an acidic solution.
  • the Fe raw material include iron metal, iron oxide, iron hydroxide, iron carbonate, iron chloride, iron iodide, iron sulfate, iron nitrate, iron phosphate, iron oxalate, and the like. It is preferable to use iron metal, iron carbonate, iron sulfate or iron chloride, and it is more preferable to use iron sulfate because it serves as a sulfur source for the precipitate containing S.
  • Ni raw material examples include nickel metal, nickel oxide, nickel hydroxide, nickel carbonate, nickel chloride, nickel iodide, nickel sulfate, nickel nitrate, nickel phosphate, and nickel oxalate. It is preferable to use nickel metal, nickel carbonate, nickel sulfate or nickel chloride, and it is more preferable to use nickel sulfate because it serves as a sulfur source for the precipitate containing S.
  • the acidic solution include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and the like. Among them, sulfuric acid is preferred because it serves as a sulfur source for the precipitate containing S, Fe and Ni.
  • concentration of the solution containing Fe and Ni can be appropriately adjusted within a range in which the Fe raw material and the Ni raw material are substantially dissolved in the acidic solution.
  • the ratio of the number of moles of Fe to the total number of moles of Fe and Ni in the solution containing Fe and Ni may be 0.4 to 0.6, preferably 0.45 to 0.55, and more preferably 0.48 to 0.52.
  • the precipitate containing Fe and Ni is obtained by reacting the solution containing Fe and Ni with the precipitant.
  • the precipitant may be added to the solution containing Fe and Ni, or the solution containing Fe and Ni may be added to the precipitant.
  • the solution containing Fe and Ni referred to here may be a solution containing Fe and Ni when reacted with the precipitant.
  • Raw materials containing Fe and Ni may be prepared as separate solutions, and the solutions may be added to react with the precipitant. Even in cases where they are prepared as separate solutions, adjustments are produced as appropriate within the range in which each raw material is substantially dissolved in the acidic solution.
  • the precipitant is not limited as long as it reacts with the solution containing Fe and Ni to obtain the precipitate.
  • the precipitant examples include oxalic acid and alkaline solutions such as an aqueous sodium hydroxide solution, an aqueous sodium hydrogen carbonate solution, an aqueous potassium hydroxide solution, and an aqueous lithium hydroxide solution.
  • the precipitate can also be obtained by blowing carbon dioxide into the solution containing Fe and Ni.
  • the precipitate include oxalate, carbonate, hydroxide, and the like.
  • the precipitation process may include a process of separating and washing the precipitate.
  • a method for separating the precipitate for example, after adding a solvent (preferably water) to the obtained precipitate and mixing it, a filtration method, a decantation method, or the like can be used.
  • washing can be performed by repeating the same process for the precipitate that has once been separated.
  • the precipitate After separating the precipitate, in order to prevent the precipitate from re-dissolving in the remaining solvent in the heat treatment of the subsequent oxidation process and aggregating the precipitate when the solvent evaporates, it is preferable to remove the solvent from the precipitate.
  • the precipitate may be dried in an oven at a temperature in a range from 70 to 200° C. for 5 to 12 hours. After drying, if necessary, the particles may be crushed or pulverized to adjust the particle size.
  • the precipitate containing S, Fe and Ni can be obtained by adding a predetermined amount of a sulfur compound as necessary during or after the reaction between the solution containing Fe and Ni and the precipitant, and can be obtained by adding a sulfur compound in the process of separating and washing.
  • the precipitate containing S, Fe and Ni can also be produced by adding a predetermined amount of a sulfur compound to the obtained precipitate, or by reacting the precipitate with the sulfur compound, as necessary.
  • the reaction between the precipitate and the sulfur compound can be performed, for example, by mixing the precipitate and the sulfur compound and then heat-treating the mixture.
  • the precipitate containing S, Fe and Ni can also be produced by sulfurizing a part of the precipitate with hydrogen sulfide gas or the like.
  • the sulfur compound is as described above.
  • the oxidation process is a process of obtaining an oxide containing Fe and Ni by heat-treating the precipitate containing Fe and Ni obtained in the precipitation process.
  • the oxidation process can convert the precipitate to the oxide, for example, by heat treatment.
  • the heat treatment of the precipitate is performed, the heat treatment must be performed in the presence of oxygen, and can be performed, for example, in an air atmosphere.
  • the non-metallic portion of the precipitate contains an oxygen atom.
  • the precipitate containing S, Fe and Ni is used in the oxidation process, the FeNi oxide-S can be obtained.
  • the obtained FeNi oxide-S may be pulverized or pulverized to adjust the particle size, as necessary.
  • the heat treatment temperature in the oxidation process (hereinafter referred to as oxidation temperature) is not particularly limited, but the heat treatment temperature can be, for example, 200 to 800° C., preferably 350 to 450° C.
  • the heat treatment time can be, for example, 4 to 24 hours, preferably 8 hours.
  • the obtained oxide is an oxide particle in which Fe and Ni are sufficiently microscopically mixed, and the shape of the precipitate, particle size distribution and the like are reflected.
  • the precipitate containing S, Fe and Ni used in the oxidation process may be synthesized during the oxidation process. Specifically, for example, the precipitate containing Fe and Ni is heat-treated under a mixed gas flow of air and hydrogen sulfide so that synthesis and oxidation of the precipitate containing S, Fe, and Ni are performed in parallel.
  • the present embodiment is different from the first embodiment in a manufacturing method of FeNiN, and the other parts are similar to those of the first embodiment. Therefore, only a part different from the first embodiment will be described below.
  • a manufacturing method of an FeNi superlattice according to the present embodiment will be described with reference to the flowchart showing in FIG. 4 .
  • the composition ratio of Fe:Ni may be about 50:50.
  • it is sufficient that the proportion of Fe is 50 ⁇ 3% and the proportion of Ni is the remaining ⁇ 100 ⁇ (50 ⁇ 3) ⁇ %.
  • FeNi powder for example, FeNi nanoparticles synthesized by the thermal plasma method manufactured by Nisshin Engineering Co., Ltd., FeNi powder synthesized by the gas atomization method manufactured by Epson Atmix, and the like can be used.
  • FeNi—S which is the FeNi alloy to which S is added.
  • a mixed gas of H 2 S gas and nitrogen (N 2 ) gas As a result, FeNi—S, which is the FeNi alloy to which S is added, is obtained.
  • 3% H 2 S gas+97% N 2 gas is used as the mixed gas, and a heat treatment is performed at 200 to 500° C. for 2 to 24 hours to obtain the FeNi—S.
  • a nitriding process is performed in the same manner as in the first embodiment to synthesize the FeNiN—S, and then a denitriding treatment is further performed to obtain the FeNi superlattice.
  • the FeNi superlattice obtained as described above also contains S. Also in this case, as shown in Examples described later, it is possible to obtain high ammonia efficiency.
  • FIG. 5 is a diagram showing how the differences in the manufacturing conditions of the FeNi superlattice, the formation rate of FeNiN, the ammonia efficiency, and the like changed in each Example and Comparative (COMP) Example.
  • (1) means the manufacturing method of the first embodiment
  • (2) means the manufacturing method of the second embodiment
  • Example 6 shows a case where the FeNi—S is synthesized by reacting the FeNi alloy particles produced by the gas atomization method of the second embodiment with ammonium sulfate.
  • Example 7 shows a case where the FeNi—S is synthesized by reacting ammonium sulfate with FeNi alloy particles produced by the thermal plasma method in the second embodiment.
  • Comparative Examples 1 and 2 show cases where FeNi produced by the thermal plasma method is subjected to the nitriding and denitriding treatment without reacting with ammonium sulfate.
  • a sulfur content (mass %) shown in FIG. 5 that is, the mass ratio of S to the total mass of Fe, Ni, and S is evaluated using a generally used elemental mass analysis method.
  • the sulfur content can be identified by inductively coupled plasma (ICP) emission spectroscopy, energy dispersive X-ray spectroscopy (EDS) using an electron microscope, or the like.
  • the sulfur content (mass %) is substantially the same before and after the nitriding and denitriding treatment.
  • the FeNiN formation rate is the ratio of the amount of FeNiN formed after the nitriding treatment to the amount of FeNi alloy before the nitriding treatment, and is calculated from the reference intensity ratio (RIR) method by measuring the powder XRD pattern. More specifically, the FeNiN formation rate is a rate of the amount of FeNiN actually obtained with respect to the ideal formation amount of FeNiN when it is assumed that the total amount of FeNi alloy contained in the raw material before the nitriding treatment is obtained as FeNiN by the nitriding treatment.
  • RIR reference intensity ratio
  • the RIR values of FeNiN, Fe 2 Ni 2 N, and FeNi alloy stored in the database of the analysis software (PDXL2) attached to the XRD device (SmartLab manufactured by Rigaku Corporation) were used for the analysis of the formation rate by the RIR method. Further, the efficiency improvement rate indicates the rate of the ammonia efficiency in each of Comparative Example 1 and Examples 1 to 7 in cases where Comparative Example 2 is used as a reference (REF).
  • the FeNiN formation rate was 95%.
  • the FeNiN formation rate was measured by an X-ray diffraction method (apparatus name: Smartlab, tube current: 200 mA, tube voltage: 45 kV) using k ⁇ rays of Fe (wavelength: 1.75653 ⁇ ), and was defined as the ratio of the integrated intensity of the FeNiN peak (40°) to the sum of the integrated intensity of the FeNiN peak and the integrated intensity of the Fe 2 Ni 2 N peak (41.5°).
  • the FeNiN formation rate was calculated using the reference intensity ratio (RIR) method by measuring the powder XRD pattern in addition to the mass of the FeNi alloy as the raw material and the mass of the obtained FeNi nitride.
  • RIR reference intensity ratio
  • the obtained FeNiN was heat-treated at 250° C. for 20 hours in a hydrogen gas atmosphere (hydrogen flow rate: 1 liter/min) to obtain an L1 0 type FeNi ordered alloy. It was confirmed that the sulfur content in the L1 0 type ordered alloy was 0.03% by mass, which was almost the same amount as in the FeNi alloy containing S obtained in the reduction process.
  • the sulfur content was measured by the ICP-AES method after dissolving the obtained FeNi alloy in hydrochloric acid, and defined as the mass ratio of S to the total mass of Fe, Ni, and S.
  • Example 2 The same processes as in Example 1 were performed except that the heat treatment temperature in the nitriding process was changed to 415° C.
  • Example 2 The same processes as in Example 2 were performed except that ammonium sulfate was added and a heat treatment was performed to the oxalate containing Fe, Ni and S obtained in Example 1. Ammonium sulfate was added in an amount of 0.02% by mass with respect to the oxalate. As a result, the sulfur content in the alloy particles was 0.05% by mass.
  • Example 2 The same processes as in Example 2 were performed except that ammonium sulfate was added and a heat treatment was performed to the oxalate containing Fe, Ni and S obtained in Example 1. Ammonium sulfate was added in an amount of 0.11% by mass with respect to the oxalate. As a result, the sulfur content in the alloy particles was 0.14% by mass.
  • Example 2 The same processes as in Example 2 were performed except that ammonium sulfate was added and a heat treatment was performed to the oxalate containing Fe, Ni and S obtained in Example 1. Ammonium sulfate was added in an amount of 0.45% by mass with respect to the oxalate. As a result, the sulfur content in the alloy particles was 0.48% by mass.
  • the temperature during the nitriding treatment was set to 300° C. In cases of FeNi to which sulfur is not added, when the temperature exceeds 300° C., the FeNiN formation rate is not stabilized, and the ammonia efficiency similarly decreases.
  • the time for the nitriding treatment was set to 40 hours. If the time is shorter than 40 hours, the FeNiN formation rate is not stabilized, and the ammonia efficiency similarly decreases.
  • the sample amount was set to 400 mg. If the amount of FeNi to be nitrided at one time is increased, the FeNiN formation rate is not stabilized, and the ammonia efficiency similarly decreases.
  • Example 1 the sulfur was as small as 0.03 (mass %), but even if the amount of NH 3 was reduced to 1 liter/min under nitriding conditions at 335° C. for 40 hours, the FeNiN formation rate was a high value of 95% and the ammonia efficiency was a high value of 22.9 ( ⁇ 10 ⁇ 5 ). The efficiency improvement rate was also a high value of 4.8.
  • Example 2 with the same sulfur content as in Example 1, only the nitriding temperature was increased to 415° C. Although the FeNiN formation rate decreased to 43%, the ammonia efficiency was 10.4 ( ⁇ 10 ⁇ 5 ) which is higher than the reference. The efficiency improvement rate was also a high value of 2.2.
  • Example 3 the sulfur content was set to 0.05 (mass %), which was higher than in Example 1, FeNiN The formation rate was as high as 97%, and the ammonia efficiency was a high value of 23.6 ( ⁇ 10 ⁇ 5 ). The efficiency improvement rate was also a high value of 4.9. As will be described later, it has been confirmed that the FeNiN formation rate can be increased by changing the temperature of the nitriding treatment according to the sulfur content. In Example 3, the nitriding temperature was set to 415° C. so as to increase the FeNiN formation rate. Therefore, the FeNiN formation rate could be a particularly high value, and a higher ammonia efficiency was obtained.
  • Example 4 the sulfur content was increased to 0.14 (mass %), which is higher than in Example 3, and the nitriding conditions were the same as in Example 3.
  • the FeNiN formation rate was maintained at a high value of 90%, and the ammonia efficiency was maintained at a high value of 21.8 ( ⁇ 10 ⁇ 5 ).
  • the efficiency improvement rate was also a high value of 4.6.
  • Example 5 to 7 the sulfur content was increased more than in Example 4, and the same nitriding conditions as in Examples 3 and 4 were used.
  • Example 5 the sulfur content was set to 0.48 (mass %), the FeNiN formation rate was 94%, the ammonia efficiency was 22.8 ( ⁇ 10 ⁇ 5 ), and the efficiency improvement rate was 4.8, all of which were high values.
  • Example 6 the sulfur content was set to 1.05 (mass %), the FeNiN formation rate was 92%, the ammonia efficiency was 22.1 ( ⁇ 10 ⁇ 5 ), and the efficiency improvement rate was 4.7, all of which were high values.
  • Example 7 the sulfur content was set to 2.26 (mass %), the FeNiN formation rate was 88%, the ammonia efficiency was 21.2 ( ⁇ 10 ⁇ 5 ), and the efficiency improvement rate was 4.5, all of which were high values.
  • FIG. 6 shows the XRD pattern measurement results for Comparative Example 2 and Example 3. Circles shown in FIG. 6 are XRD diffraction peaks attributable to FeNiN. It can be seen that in both Comparative Example 2 and Example 3, high-purity FeNiN was obtained.
  • the ammonia efficiency can be improved by a factor of 2 or more compared to the conventional manufacturing method. Therefore, in the FeNi superlattice of the present embodiment, by increasing the ammonia efficiency, at least one of reducing the amount of NH 3 , shortening the nitriding time, and increasing the amount of material to be nitrided at one time can be performed, which reduces costs.
  • FIGS. 7 A to 7 D show the results shown in FIGS. 7 A to 7 D.
  • FIG. 7 A shows the result of cross-sectional TEM observation
  • FIG. 7 B shows a S composition image
  • FIG. 7 C shows an Fe composition image
  • FIG. 7 D shows a Ni composition image.
  • a particle diameter of the FeNi superlattice was about 100 nm, but the particle diameter can be appropriately changed according to the purpose of applying the FeNi superlattice, and can be changed, for example, in the range of 100 nm to several ⁇ m.
  • the particle diameter of the FeNi superlattice changes according to the sintering temperature for obtaining the FeNi oxide and the reduction temperature for obtaining the FeNi alloy, and there is a tendency that the particle diameter tends to increase with increase in temperature. Since changes in particle diameter affect magnetic properties and environmental resistance, the sintering temperature and reduction temperature should be set according to the purpose of application of the FeNi superlattice so that the desired magnetic properties and environmental resistance can be obtained.
  • FIG. 8 A shows the result of cross-sectional TEM observation
  • FIG. 8 B shows a S composition image
  • FIG. 8 C shows an Fe composition image
  • FIG. 8 D shows a Ni composition image.
  • FIG. 9 is a diagram showing the results.
  • Example 4 is the same as Example 4 in FIG. 5 .
  • Examples 9 and 10 and Comparative Examples 9 and 10 show cases in which only the temperature of the nitriding treatment is changed from Example 4.
  • Comparative Example 2 is the same as Comparative Example 2 in FIG. 5 .
  • Comparative Examples 3 to 6 show cases in which only the temperature of the nitriding treatment is changed from Comparative Example 2, and the NH 3 flow rate remains at 5 liters/min.
  • the heat treatment temperature of the nitriding treatment was 325° C. and 500° C. as shown in Comparative Examples 9 and 10, the FeNiN formation rates were 12% and 3%, respectively, and the ammonia efficiencies were 2.9 ( ⁇ 10 ⁇ 5 ) and 0.72 ( ⁇ 10 ⁇ 5 ), respectively. The efficiency improvement rates were 0.61 and 0.15, respectively. From these results, it can be seen that, in cases where 0.14% by mass of S is added, the ammonia efficiency and efficiency improvement rate are increased by setting the temperature of the nitriding treatment to a temperature range higher than 325° C. and lower than 500° C. More preferably, it can be seen that the ammonia efficiency and efficiency improvement rate can be increased by setting the nitriding temperature in the temperature range from 375 to 450° C.
  • the FeNiN formation rates were 99% and 95%, respectively, and the ammonia efficiencies were 4.7 ( ⁇ 10 ⁇ 5 ) and 4.6 ( ⁇ 10 ⁇ 5 ).
  • the efficiency improvement rates were 1 and 0.98, respectively.
  • the desired ammonia efficiency and efficiency improvement rate can be obtained by setting the temperature of the nitriding treatment to at least a temperature range from 375 to 450° C.
  • the desired ammonia efficiency and efficiency improvement rate cannot be obtained unless the temperature of the nitriding treatment is at least in the temperature range from 300 to 325° C. Therefore, by adding S, it is possible to widen the temperature range in which the desired ammonia efficiency and efficiency improvement rate can be obtained, and it is also possible to raise the process temperature and expand the process window.
  • the process temperature can be raised, the FeNiN—S can be synthesized at a higher temperature, so that the crystallinity of the FeNi superlattice can be improved. Accordingly, properties of the FeNi superlattice can be improved. Further, if the process window can be expanded, the temperature of the nitriding treatment can be set within the range of the process window, which facilitates temperature control.
  • Example 1 The above has described examples in which the sulfur content is 0.14 mass % as in Example 4, and the temperature of the nitriding treatment should be at least in the temperature range from 375 to 450° C. based on the results of Examples 4, 9 and 10.
  • FIG. 10 is a diagram showing the results.
  • Example 3 is the same as Example 3 in FIG. 5 .
  • Examples 12 and 13 show cases in which only the time of the nitriding treatment is changed from Example 3.
  • Comparative Example 2 is the same as Comparative Example 2 in FIG. 5 .
  • Comparative Examples 7 and 8 show cases in which only the time of the nitriding treatment is changed from Comparative Example 2.
  • the coercive force of Example 3 was 135 kA/m
  • the coercive force of Example 7 was 120 kA/m.
  • the saturation magnetization of Comparative Example 2 was 139 Am 2 /kg and the saturation magnetization of Example 3 was also 139 Am 2 /kg.
  • the saturation magnetization of Example 7 was 91 Am 2 /kg. From these results, it can be seen that the FeNi superlattice to which an appropriate amount of S is added as in Example 3 has the same performance as the FeNi superlattice to which S is not added as in Comparative Example 2. Since an excessive amount of sulfur causes a decrease in saturation magnetization as in Example 7, the sulfur content is preferably 2% by mass or less from the viewpoint of magnetic performance.
  • the inventors examined the oxidation number of sulfur contained in the FeNi superlattice magnetic powders obtained in Examples 3 and 4, respectively. Specifically, XAFS measurement (that is, partial fluorescence yield measurement) was performed at Aichi Synchrotron Light Center BL6N1 in the following procedure.
  • the sample was embedded in an indium sheet and attached to a sample holder using conductive carbon tape.
  • the sample holder to which the sample was attached was introduced into the He atmospheric pressure chamber, and He substitution was performed for about 30 minutes before measurement.
  • Partial fluorescence yield measurements were performed in the measurement range of 2440 to 2550 eV.
  • the incident angle of the incident light was 20° with respect to the sample plate.
  • the present inventors analyzed the measurement results using “Athena” as analysis software. Flattening and normalization were performed by setting the end E0 of 2471 eV, the pre-edge range of 2440 to 2470 eV, and the normalization range of 2508 to 2547 eV. Then, the presence or absence of an absorption peak due to S 6+ and an absorption peak due to S 2 ⁇ was determined by comparison with standard samples. The presence or absence of the absorption peaks was determined by the rise of the absorption intensity at 10 times or more the noise level (that is, the S/N ratio of 10 or more). This noise level is the mean value of the absolute value of the deviation of the signal in the range of 2440 to 2460 eV in the pre-edge range.
  • FIG. 12 is a diagram showing X-ray absorption near edge spectra (XANES) for FeNi superlattice magnetic powder of each of Example 3 and Example 4.
  • FIG. 12 also shows the X-ray absorption near-edge spectra of (NH 4 ) 2 SO 4 and FeS as the standard samples.
  • the oxidation number of sulfur was a mixture of S 2 ⁇ and S 6+ .
  • Example 3 contained more S 6+ than Example 4.
  • Example 4 contained more S 2 ⁇ than Example 3. Incidentally, although not shown, it has been confirmed that the oxidation numbers of sulfur before and after the denitriding treatment are substantially the same in each of Examples 3 and 4.
  • S is doped to the FeNi oxide in the first embodiment, and S is doped to the FeNi alloy in the second embodiment, but the doping of S may be performed during the nitriding treatment.
  • S may be doped at the stage of the Fe, Ni salt or the FeNi alloy.
  • S may be doped during the nitriding treatment.
  • the doping method of S is not limited to the methods described in the first and second embodiments, and any method can be used.
  • ammonium sulfate may be added to the raw material and then a heat treatment may be performed, or H 2 S may be applied to the raw material.
  • FeNi—S can be synthesized by any method, such as adding ammonium sulfate to metal FeNi or performing immersion nitriding by mixing H 2 S with NH 3 gas during nitriding.
  • S segregates in the FeNi superlattice.
  • S segregates on the surface of the particles of the FeNi superlattice.
  • S may segregate to a portion other than the surface.
  • S may be segregated inside the particles of the FeNi superlattice.
  • an L1 0 type FeNi ordered alloy has an L1 0 type ordered structure and contains sulfur.
  • a sulfur content of the L1 0 type FeNi ordered alloy according to the first aspect is 0.01% by mass or more.
  • the sulfur content of the L1 0 type FeNi ordered alloy according to the first aspect or the second aspect is 10% by mass or less.
  • the L1 0 type FeNi ordered alloy according to any one of the first to third aspects is composed of particles 100 having the L1 0 type ordered structure, and the sulfur is present throughout the particles.
  • the L1 0 type FeNi ordered alloy according to any one of the first to third aspects is composed of particles 100 having the L1 0 type ordered structure, and the sulfur is segregated to the particles.
  • the sulfur is segregated on surfaces of the particles.
  • an oxidation number of the sulfur includes S 2 ⁇ or S 6+ or a mixed state of S 2 ⁇ and S 6+ .
  • a manufacturing method of an L1 0 type FeNi ordered alloy includes performing a nitriding treatment to an FeNi alloy containing sulfur to obtain a nitride containing Fe and Ni.
  • a sulfur content in the FeNi alloy is 0.01% by mass or more.
  • a sulfur content in the FeNi alloy is 10% by mass or less.
  • the nitriding treatment includes a heat treatment at a temperature in a range from 300 to 500° C.
  • the nitriding treatment includes a heat treatment at a temperature in a range from 330 to 450° C.
  • a nitriding efficiency in the nitriding treatment to obtain the nitride containing Fe and Ni is greater than 4.7 ⁇ 10 ⁇ 5 .

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