CN110473704B - 一种薄型片式稀土永磁材料的制备方法 - Google Patents

一种薄型片式稀土永磁材料的制备方法 Download PDF

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CN110473704B
CN110473704B CN201910862926.4A CN201910862926A CN110473704B CN 110473704 B CN110473704 B CN 110473704B CN 201910862926 A CN201910862926 A CN 201910862926A CN 110473704 B CN110473704 B CN 110473704B
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杨维铭
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Anji Hongming Magnetic Equipment Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047Alloys characterised by their composition
    • H01F1/053Alloys characterised by their composition containing rare earth metals
    • H01F1/055Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0576Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together pressed, e.g. hot working
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00Apparatus 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
    • H01F41/02Apparatus 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
    • H01F41/0253Apparatus 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00Apparatus 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
    • H01F41/02Apparatus 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
    • H01F41/0253Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0266Moulding; Pressing
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00Apparatus 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
    • H01F41/02Apparatus 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
    • H01F41/0253Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0293Apparatus 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 diffusion of rare earth elements, e.g. Tb, Dy or Ho, into permanent magnets

Abstract

本发明提高一种薄型片式稀土永磁材料的制备方法,涉及磁性材料技术领域。一种薄型片式稀土永磁材料的制备方法,包括以下步骤:(1)主相合金的制备,将分别含有钕、镝、铁、硼的物质混炼以后制备成主相合金,然后进行粉碎、研磨、过筛,得到主相合金粉;(2)晶界相合金的制备,将分别含有钕、Co、Mo、硼、铁的物质混炼,以后进行速凝固,淬速为27‑35m/s,制备成晶界合金,然后粉碎,得到晶界相合金粉;(3)将主相合金粉、晶界相合金粉、氧化镁、氧化锌混合均匀后进行模压成型,压成片状生胚,再进行烧结,回火以后冷却得到薄型片式稀土永磁材料。本发明的薄型片式稀土永磁材料的制备方法,制备的稀土永磁材料磁性优良,抗弯强度高,耐腐性强。

Description

一种薄型片式稀土永磁材料的制备方法
技术领域
本发明涉及磁性材料技术领域,具体涉及一种薄型片式稀土永磁材料的制备方法。
背景技术
永磁材料又称“硬磁材料”。一经磁化即能保持恒定磁性的材料。具有宽磁滞回线、高矫顽力和高剩磁。实用中,永磁材料工作于深度磁饱和及充磁后磁滞回线的第二象限退磁部分。常用的永磁材料分为铝镍钴系永磁合金、铁铬钴系永磁合金、永磁铁氧体、稀土永磁材料和复合永磁材料。
永磁材料包括铁氧体永磁、稀土永磁(稀土钴、钕铁硼等)、铝镍钴、铁铬钴、铝铁等材料,其中最常用、用量最大的是铁氧体永磁、钕铁硼稀土永磁。
铁氧体永磁在永磁材料中,尽管综合磁性能较低,但与金属永磁相比,电阻率高,稳定性好,耐环境变化强,原料来源丰富、性能价格比较高、工艺成熟,又不存在氧化问题,故在永磁材料的诸多应用领域,仍是最理想的首选永磁材料。铁氧体永磁自50年代批量生产以来,其发展势头十分迅猛,目前产值约为稀土永磁的1.5倍,预计今后较长一段时间内,它仍将是应用最广、需求量最大的永磁材料。
同时,铁氧体永磁及其应用产品还是典型的节能、节材、节汇和出口创汇产品。无论从资源利用角度,还是从能源和应用的角度来看,其发展前景都十分广阔。发展铁氧体永磁对发展中国汽车、摩托车、电子信息等国民经济支柱产业及出口创汇具有重大意义,符合国家产业政策与规划,随着电子信息技术迅速发展,国内外对高性能铁氧体永磁的市场需求越来越大。
永磁材料的应用与研究开始于十九世纪末。随着人们对物质磁性研究的深入以及各种制造工艺水平的提高,永磁材料的研究主要包括金属合金磁体、铁氧体磁性材料和稀土永磁材料三个阶段。其中,金属合金磁体和铁氧体磁性材料虽然具有成本低廉,原材料丰富的优势,但是其最大磁能积(BH)max一般小于10MGOe,磁性较差,因而逐渐被稀土永磁材料所取代。
现有技术中的永磁材料的抗弯强度低,耐磨性差,抗腐蚀能力有限,在长久使用的时候晶界处会容易腐蚀,长期使用时会破坏磁性,缩短使用寿命。
发明内容
有鉴于此,本发明提供一种薄型片式稀土永磁材料的制备方法,包括以下步骤:
(1)主相合金的制备,将分别含有钕、镝、铁、硼的物质混炼以后制备成主相合金,然后进行粉碎、研磨、过筛,得到主相合金粉;
(2)晶界相合金的制备,将分别含有钕、Co、Mo、硼、铁的物质混炼,以后进行速凝固,淬速为27-35m/s,制备成晶界合金,然后粉碎,得到晶界相合金粉;
(3)将主相合金粉、晶界相合金粉、氧化镁、氧化锌混合均匀后进行模压成型,压成片状生胚,再进行烧结,回火以后冷却得到薄型片式稀土永磁材料。
较为有选的,步骤(1)所述含有钕、镝、铁、硼的物质为钕、镝、铁、硼的单质或其氧化物。
较为有选的,步骤(2)所述含有钕、Co、Mo、硼、铁的物质为钕、Co、Mo、硼、铁的单质及其氧化物中的一种或两种。
较为有选的,所述主相合金中按重量份计包括单质钕11-13份、镝0.4-0.7份、铁65-73份、硼4-6份。
较为有选的,晶界相合金中按重量份计包含单质钕26-28份、Co 0.5-1份、Mo 0.5-1份、硼4.3-5.5份、铁45-52份。
较为有选的,步骤(3)所述的主相合金粉、晶界相合金粉、氧化镁、氧化锌的质量比为10:0.6-1.5:0.3-0.8:0.4-0.8。
较为有选的,所述烧结为将生胚放入真空炉中,以3-5℃的升温速度进行升温,升温至1130-1150℃,保温2-3h。
较为有选的,所述回火为将经过烧结的生坯升温至860-910℃,保温30min,冷却后再升温至570-590℃保温2-3h后冷却至室温。
本申请中晶界相合金在烧结的时候能够显著提高烧结体的抗弯强度,添加晶界合金能够使磁体中晶界相的分布更加均匀,基本主晶相在烧结过程中晶粒之间的直接接触,抑制晶粒的不规则长大,晶粒均匀化有利于提高抗弯强度。晶界相合金的制备采用速凝的方式能够很好抑制晶粒的二次长大,优化晶界合金的制备。
本申请中主相合金粉、晶界相合金粉的制备参数可以参考现有技术中合金的制备方法中的参数。
主体使用钕、镝、铁、硼的配合能够使磁体具有很好的磁性。
在钕、铁、硼稀土永磁材料中添加稀土元素镝,能够改善材料整体的耐腐蚀能力,在晶界上形成金属间化合物。尤其是晶界相中少量的Co,在晶界中形成含Co的富钕相的金属间化合物,Mo,则能够在晶界上与铁、硼形成金属间化合物,金属间化合物能够在晶界上偏析,提高永磁材料的耐酸碱性。另外,少量的氧化锌、Co等的引入可以降低富钕相的化学性质,细化网状富钕晶界相的厚度,使晶间腐蚀发生的通道变窄,增大富钕边界相的电阻,降低电化学腐蚀的速度,但是氧化锌、Co的添加量一定不能过多,以免影响稀土永磁材料的磁性。氧化镁的添加能够有助于烧结过程中晶粒的细化,烧结的时候能够起到粘结的作用,增强磁体的强度和耐腐蚀性。
本发明的薄型片式稀土永磁材料的制备方法,制备的稀土永磁材料磁性优良,抗弯强度高,耐腐性强。
具体实施方式
下面结合具体实施方式对本发明进行详细描述。
实施例1
一种薄型片式稀土永磁材料的制备方法,包括以下步骤:
(1)主相合金的制备,将单质钕11份、单质镝0.4份、单质铁65份、单质硼4份混炼以后制备成主相合金,然后进行粉碎、研磨、过筛,得到主相合金粉;
(2)晶界相合金的制备,将单质钕26份、Co 0.5份、Mo 0.5份、硼4.3份、铁45份混炼以后进行速凝固,淬速为27m/s,制备成晶界合金,然后粉碎,得到晶界相合金粉;
(3)将主相合金粉、晶界相合金粉、氧化镁、氧化锌按照质量比为10:0.6:0.3:0.4的比例混合均匀后进行模压成型,压成片状生胚,将生胚放入真空炉中,以3℃的升温速度进行升温,升温至1130℃,保温2h。经过烧结的生坯升温至860℃,保温30min,冷却后再升温至570℃保温2h后冷却至室温,得到薄型片式稀土永磁材料。
实施例2
一种薄型片式稀土永磁材料的制备方法,包括以下步骤:
(1)主相合金的制备,将单质钕13份、单质镝0.7份、氧化铁73份、单质硼6份混炼以后制备成主相合金,然后进行粉碎、研磨、过筛,得到主相合金粉;
(2)晶界相合金的制备,将单质钕28份、Co 1份、Mo 1份、硼5.5份、氧化铁52份混炼以后进行速凝固,淬速为35m/s,制备成晶界合金,然后粉碎,得到晶界相合金粉;
(3)将主相合金粉、晶界相合金粉、氧化镁、氧化锌按照质量比为10: 1.5: 0.8:0.8的比例混合均匀后进行模压成型,压成片状生胚,将生胚放入真空炉中,以5℃的升温速度进行升温,升温至1150℃,保温3h。经过烧结的生坯升温至910℃,保温30min,冷却后再升温至590℃保温3h后冷却至室温,得到薄型片式稀土永磁材料。
实施例3
一种薄型片式稀土永磁材料的制备方法,包括以下步骤:
(1)主相合金的制备,将单质钕12份、单质镝0.5份、氧化铁70份、单质硼5份混炼以后制备成主相合金,然后进行粉碎、研磨、过筛,得到主相合金粉,主相合金中按重量份计包括。;
(2)晶界相合金的制备,将钕27份、Co 0.6份、Mo 0.7份、硼5份、铁47份混炼以后进行速凝固,淬速为30m/s,制备成晶界合金,然后粉碎,得到晶界相合金粉;
(3)将主相合金粉、晶界相合金粉、氧化镁、氧化锌按照质量比为10:1:0.5:0.5的比例混合均匀后进行模压成型,压成片状生胚,将生胚放入真空炉中,以4℃的升温速度进行升温,升温至1140℃,保温2.5h。经过烧结的生坯升温至900℃,保温30min,冷却后再升温至580℃保温2.5h后冷却至室温,得到薄型片式稀土永磁材料。
对实施例1至3中的薄型片式稀土永磁材料进行性能测试,测试其抗弯强度、磁能积、矫顽力,测试结果如下:
Figure DEST_PATH_IMAGE002
表中的数据可以看出实施例1至3制备的磁体的强度很高,具有良好的磁性。
本发明的薄型片式稀土永磁材料的制备方法,制备的稀土永磁材料磁性优良,抗弯强度高,耐腐性强,长时间使用的情况下较难出现磁性下降。
本发明不局限于上述具体的实施方式,本发明可以有各种更改和变化。凡是依据本发明的技术实质对以上实施方式所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围。

Claims (2)

1.一种薄型片式稀土永磁材料的制备方法,其特征在于,包括以下步骤:
(1)主相合金的制备,将分别含有按重量份计11-13份单质钕、0.4-0.7份单质镝、70-73份氧化铁、4-6份单质硼的物质混炼以后制备成主相合金,然后进行粉碎、研磨、过筛,得到主相合金粉;
(2)晶界相合金的制备,将分别含有按重量份计26-28份单质钕、0.5-1份单质Co、0.5-1份单质Mo、4.3-5.5份单质硼、52份氧化铁的物质混炼,以后进行速凝固,淬速为27-35m/s,制备成晶界合金,然后粉碎,得到晶界相合金粉;
(3)将主相合金粉、晶界相合金粉、氧化镁、氧化锌混合均匀后进行模压成型,压成片状生坯,再进行烧结,回火以后冷却得到薄型片式稀土永磁材料,所述主相合金粉、晶界相合金粉、氧化镁、氧化锌的质量比为10:0.6-1.5:0.3-0.8:0.4-0.8。
2.根据权利要求1 所述的一种薄型片式稀土永磁材料的制备方法,其特征在于,所述回火为将经过烧结的生坯升温至860-910℃,保温,冷却后再升温至570-590℃保温2-3h后冷却至室温。
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