CN105861908B - 一种永磁材料的制备方法 - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000010791 quenching Methods 0.000 claims abstract description 15
- 230000000171 quenching effect Effects 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 238000005496 tempering Methods 0.000 claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 229910001566 austenite Inorganic materials 0.000 claims abstract description 5
- 229910000859 α-Fe Inorganic materials 0.000 claims description 14
- 238000005915 ammonolysis reaction Methods 0.000 claims description 7
- 238000011109 contamination Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 229910001337 iron nitride Inorganic materials 0.000 abstract description 4
- 229910000734 martensite Inorganic materials 0.000 abstract description 3
- 229910000920 Fe16N2 Inorganic materials 0.000 description 11
- 238000000137 annealing Methods 0.000 description 4
- 229910017389 Fe3N Inorganic materials 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 229910000727 Fe4N Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KPLQYGBQNPPQGA-UHFFFAOYSA-N cobalt samarium Chemical compound [Co].[Sm] KPLQYGBQNPPQGA-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/16—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on nitrides
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/04—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering with simultaneous application of supersonic waves, magnetic or electric fields
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
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Abstract
本发明涉及一种取向氮化铁永磁材料的磁场热处理制备方法。该方法将表面清洁的α‑Fe薄片置于热处理炉中，通入氮气，在650~800℃保温0.5~20h，以形成氮的奥氏体γ相；待完全氮化后将合金从炉中取出，在温度低于0℃时淬火；淬火后的样品在磁场热处理炉中100~180℃回火4~100h，磁场强度为0.1~2T。该方法既可以大批量制备氮化铁材料，又可以通过磁场回火，使低温马氏体回火析出α"‑Fe16N2相时产生晶体学取向，进而获得沿磁场方向的高取向度。
Description
技术领域
本发明涉及一种永磁材料的制备方法，属于材料制备领域。
背景技术
铁氮化工艺最初的应用目的是提高钢铁的耐腐蚀性能和硬度，最近的研究发现铁氮化物具有某些优异的磁性能而引起广泛的关注。随氮含量的变化，氮化铁具有不同的结构和性能，主要包括间隙固溶体（α，γ，ε），化合物相（γ´-Fe4N，ε-Fe3N）和介稳相(α´-马氏体和α"-Fe16N2)。所有氮化铁都为亚稳相，会分解成Fe和N2。但在400℃以下其分解的动力学过程非常缓慢，受动力学过程限制，氮化铁相在室温可以稳定存在。这其中α"-Fe16N2的饱和磁化强度值为 2.83 T，远高于其他材料，引起人们浓厚的兴趣。
α"-Fe16N2最早是在1951年发现的。Jack用X射线衍射方法研究Fe-N二元合金系统的相图时，在富铁的一边，发现了一种新的亚稳态相，即具有体心四方晶格结构的α"-Fe16N2相。Jack的做法是将铁粉末在700~750℃下进行氮化反应，得到含氮奥氏体γ相，然后对奥氏体进行急速冷却得到α´-马氏体，再在120℃下经过长时间回火，最后得到α+α"-Fe16N2或α+α"-Fe16N2+γ的混合相。得到的混合相中α"-Fe16N2的含量不超过50%。
多年来，众多科学家使用了多种方法，如：氮化退火法、共析法、离子注入法、化学气相沉积法，物理气相沉积法等。然而令人遗憾的是一直未能成功的制备单相的α"-Fe16N2。一个可能的原因是：α"-Fe16N2是亚稳相，在温度超过200℃时易分解为α+γ´-Fe4N。而Fe4N，Fe3N是稳定的相，在用传统的薄膜沉积技术制备Fe-N薄膜的过程中，具有较低饱和磁化强度的Fe4N，Fe3N化合物比亚稳相α"-Fe16N2更易形成，所以制备纯单相α"-Fe16N2是比较困难的。1989 年，日本日立研究所的 Sugita 等人用分子束外延法在In0.2Ga0.8As(001)单晶基片上成功制备出α"-Fe16N2单晶薄膜，并用振动样品磁强计测得其饱和磁化强度值为2.9T。
因此虽然出现了一系列制备α"-Fe16N2相的方法，但制备单相的α"-Fe16N2相依然困难。现在制备α"-Fe16N2材料最主要的方法还是最早采用的方法：氮化退火法。因此，如何在现有技术的基础上提高材料的磁性就比较关键。
鉴于以上，本发明的目的是采用磁场热处理退火的方式，获得有序取向的α"-Fe16N2相，进而提高氮化铁材料的磁性。
发明内容
本发明是采用磁场热处理退火的方式，获得一种高性能氮化铁永磁材料的制备方法。
本发明的具体步骤为：
1）材料准备
准备α-Fe薄片，清除表面污染，保持表面清洁；
2）高温氮化
将α-Fe薄片置于热处理炉中，以恒定的速率通入氮气；待完全排出空气后，以5℃/min的速度升温至650~800℃；保温0.5~20h，以形成氮的奥氏体γ相；
3）淬火
将完全氮化后的合金从炉中取出，在温度低于0℃时淬火；
4）磁场热处理
将淬火后的样品在磁场热处理炉中，在100~180℃回火，保持4~100h，磁场强度为0.1~2T；磁场可以由永磁体产生，也可以由电磁铁产生，但高强磁场只能通过电磁铁获得。
本发明的优点是：
1）可以大批量制备氮化铁材料；
2）通过磁场回火，使低温马氏体回火析出α"-Fe16N2相时产生晶体学取向，进而获得沿磁场方向的高取向度。
具体实施方式
下面结合实施例对本发明进行详细描述，以便更好地理解本发明的目的、特点和优点。虽然本发明是结合该具体的实施例进行描述，但并不意味着本发明局限于所描述的具体实施例。相反，对可以包括在本发明权利要求中所限定的保护范围内的实施方式进行的替代、改进和等同的实施方式，都属于本发明的保护范围。对于未特别标注的工艺参数，可按常规技术进行。
本发明的具体步骤为：
1）材料准备
准备α-Fe薄片，清除表面污染，保持表面清洁；
2）高温氮化
将α-Fe薄片置于热处理炉中，以恒定的速率通入氮气；待完全排出空气后，以5℃/min的速度升温至650~800℃；保温0.5~20h，以形成氮的奥氏体γ相；
3）淬火
将完全氮化后的合金从炉中取出，在温度低于0℃时淬火；
4）磁场热处理
将淬火后的样品在磁场热处理炉中，在100~180℃回火，保持4~100h，磁场强度为0.1~2T；磁场可以由永磁体产生，也可以由电磁铁产生，但高强磁场只能通过电磁铁获得。
通过本发明可以制备沿外磁场方向具有高取向度的氮化铁磁体，在取向方向具有出色的磁性能。
实施例1：
本发明的步骤为：
1）材料准备
准备α-Fe薄片，清除表面污染，保持表面清洁；
2）高温氮化
将α-Fe薄片置于热处理炉中，以恒定的速率通入氮气；待完全排出空气后，以5℃/min的速度升温至650℃；保温20h；
3）淬火
将完全氮化后的合金从炉中取出，在温度低于0℃时淬火；
4）磁场热处理
将淬火后的样品在磁场热处理炉中，在100℃回火，保持100h，磁场强度为0.1T；磁场由钐钴永磁体产生。
对实施例1所制备的样品进行XRD表征，检测到了α"-Fe16N2相，并且沿磁场方向具有取向性。
实施例2：
本发明的步骤为：
1）材料准备
准备α-Fe薄片，清除表面污染，保持表面清洁；
2）高温氮化
将α-Fe薄片置于热处理炉中，以恒定的速率通入氮气；待完全排出空气后，以5℃/min的速度升温至700℃；保温10h；
3）淬火
将完全氮化后的合金从炉中取出，在温度低于0℃时淬火；
4）磁场热处理
将淬火后的样品在磁场热处理炉中，在120℃回火，保持60h，磁场强度为0.8T；磁场由电磁铁产生。
对实施例2所制备的样品进行XRD表征，检测到了α"-Fe16N2相，并且沿磁场方向具有取向性。
实施例3：
本发明的步骤为：
1）材料准备
准备α-Fe薄片，清除表面污染，保持表面清洁；
2）高温氮化
将α-Fe薄片置于热处理炉中，以恒定的速率通入氮气；待完全排出空气后，以5℃/min的速度升温至750℃；保温4h；
3）淬火
将完全氮化后的合金从炉中取出，在温度低于0℃时淬火；
4）磁场热处理
将淬火后的样品在磁场热处理炉中，在140℃回火，保持20h，磁场强度为1.2T；磁场由电磁铁产生。
对实施例3所制备的样品进行XRD表征，检测到了α"-Fe16N2相，并且沿磁场方向具有取向性。
实施例4：
本发明的步骤为：
1）材料准备
准备α-Fe薄片，清除表面污染，保持表面清洁；
2）高温氮化
将α-Fe薄片置于热处理炉中，以恒定的速率通入氮气；待完全排出空气后，以5℃/min的速度升温至800℃；保温0.5h；
3）淬火
将完全氮化后的合金从炉中取出，在温度低于0℃时淬火；
4）磁场热处理
将淬火后的样品在磁场热处理炉中，在180℃回火，保持4h，磁场强度为2T；磁场由电磁铁产生。
对实施例4所制备的样品进行XRD表征，检测到了α"-Fe16N2相，并且沿磁场方向具有取向性。
Claims (1)
1.一种永磁材料的制备方法，其特征在于该方法包括以下步骤：
1）材料准备
准备α-Fe薄片，清除表面污染，保持表面清洁；
2）高温氮化
将α-Fe薄片置于热处理炉中，以恒定的速率通入氮气；待完全排出空气后，以5℃/min的速度升温至700~800℃；保温0.5~20h，以形成氮的奥氏体γ相；
3）淬火
将完全氮化后的合金从炉中取出，在温度低于0℃时淬火；
4）磁场热处理
将淬火后的样品在磁场热处理炉中，在100~180℃回火，保持4~100h，磁场强度为0.1~2T；磁场可以由永磁体产生，也可以由电磁铁产生，但高强磁场只能通过电磁铁获得。
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