CN114380589B - 一种高性能永磁铁氧体的制备方法 - Google Patents

一种高性能永磁铁氧体的制备方法 Download PDF

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CN114380589B
CN114380589B CN202011129056.9A CN202011129056A CN114380589B CN 114380589 B CN114380589 B CN 114380589B CN 202011129056 A CN202011129056 A CN 202011129056A CN 114380589 B CN114380589 B CN 114380589B
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ball milling
slurry
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permanent magnetic
presintering
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CN114380589A (zh
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唐少春
陆洪彬
雷成龙
涂巍巍
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HAIAN INSTITUTE OF HIGH-TECH RESEARCH NANJING UNIVERSITY
Nanjing University
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Nanjing University
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Abstract

本申请公开了一种高性能永磁铁氧体的制备方法，依次包括如下步骤：S1制备预烧料、S2掺杂添加剂、S3球磨制备料浆、S4压制成型、S5烧结、S6后处理。本发明以低含量的La‑Co取代为主配方设计，通过合适的工艺，引入多元微量添加剂，制备出高性能的永磁铁氧体。生产出来的产品具有较高的磁性能，剩磁Br≥4300Gs、磁感矫顽力Hcb≥3900Oe、内禀矫顽力Hcj≥4100Oe、磁能积BH≥4.2MGOe，达到日本TDK公司FB6B牌号指标要求。

Description

一种高性能永磁铁氧体的制备方法
技术领域
本申请涉及磁性材料技术领域，具体涉及一种高性能永磁铁氧体的制备方法。
背景技术
永磁铁氧体是以Fe2O3为主要原料，通过陶瓷工艺方法制备而成，永磁铁氧体磁性能指标主要有剩磁、矫顽力和磁能积。这三个指标越高，永磁铁氧体性能越好。剩磁与矫顽力相互影响，提高剩磁容易导致矫顽力降低，反之提高矫顽力则容易导致剩磁降低，磁能积与剩磁和矫顽力均有关。
随着物联网、新能源汽车、风力发电等新兴产业的快速发展，高性能永磁铁氧体呈现出巨大应用前景。为了满足市场需求，开发高性能永磁铁氧体已成为国内永磁铁氧体行业的首要任务。
La-Co系永磁铁氧体材料是目前应用较广的一类高性能永磁铁氧体材料，近年来，由于稀土材料镧和钴的价格一路高歌猛进，使得高性能永磁铁氧体的制备成本大大提高。
中国专利CN101351853B公开了一种氧化物磁性材料，以具有六方晶系结构的铁氧体为主相，氧化物磁性材料中所含有的金属元素用式Ca1-x-x′LaxSrx′Fe2n-yCoy表示，且表示原子比率的x、x′、y 以及表示摩尔比的n满足0.4≤ x ≤0.6、0.01 ≤x′≤0.3、0.2 ≤y≤0.45、5.2 ≤n≤ 5.8 的关系。从而获得比现有的SrLaCo铁氧体和CaLaCo铁氧体材料性能更优异的铁氧体材料，内禀矫顽力Hcj大于4500Oe，但该技术镧和钴掺杂比例高。
发明内容
本发明的目的在于提供一种高性能永磁铁氧体的制备方法，以低含量的La-Co取代为主配方设计，通过合适的工艺，引入多元微量添加剂，制备出高性能的永磁铁氧体。
为实现上述目的，本发明提供如下技术方案：
本申请实施例公开了一种高性能永磁铁氧体的制备方法，依次包括如下步骤：
S1制备预烧料：按配方LaxSr1-xO·n[（Fe1-yCoy）2O3]称取碳酸锶SrCO3、氧化镧La2O3、氧化钴Co2O3和氧化铁Fe2O3，其中n=5.9～6.1、x=0.10～0.15、y=0.08～0.13，混合原料后，以氧化锆球为球磨介质进行湿式球磨，将球磨料浆烘干后，置于预烧料窑炉内烧结，得到预烧料；
S2 掺杂添加剂：添加所述预烧料重量0.6～1.0％的CaCO3、0.2～0.6％的Cr2O3、0.2～0.6％的Bi2O3、0.1～0.4％的Al2O3、0.3～0.7％的H3BO3作为添加剂，添加所述预烧料重量0.1～0.3％的葡萄糖酸钙和0.1～0.3％的异丁烯-马来酸酐共聚物作为分散剂；
S3 球磨制备料浆：将步骤S2所得物料以氧化锆球为球磨介质进行湿式球磨，将球磨后料浆脱水得低含水量的料浆；
S4 压制成型：采用湿式成型液压机压制样品，压制压强≥100MPa，取向磁场≥8000Oe，得到生坯；
S5 烧结：将步骤S4中制备的生坯放在推板窑上烧结，烧结温度1200～1260℃，保温时间80～120 min；
S6 后处理：将步骤S5烧结出来的生坯磨削、清洗、检测，得到产品。
所述异丁烯-马来酸酐共聚物是一种具有两性的聚合物，结构中异丁烯段具有强烈的亲油性，马来酸酐段具有较好的亲水性；以葡萄糖酸钙和异丁烯-马来酸酐共聚物作为分散剂，可以提高料浆的取向度。
优选的，在上述高性能永磁铁氧体的制备方法中，步骤S1中，球磨料浆粒度控制在≤8μm；预烧温度控制在1200～1300℃；预烧保温时间控制在2～3h。
优选的，在上述高性能永磁铁氧体的制备方法中，步骤S2中，添加剂CaCO3、Cr2O3、Bi2O3、Al2O3、H3BO3的添加量分别为所述预烧料重量的0.7～0.9％、0.3～0.5％、0.3～0.5％、0.1～0.3％、0.4～0.6％。
优选的，在上述高性能永磁铁氧体的制备方法中，步骤S2中，分散剂葡萄糖酸钙和异丁烯-马来酸酐共聚物的添加量分别为所述预烧料重量的0.2～0.3％和0.1～0.2％。
优选的，在上述高性能永磁铁氧体的制备方法中，步骤S3中，球磨后料浆粒度控制在≤0.75μm。
优选的，在上述高性能永磁铁氧体的制备方法中，步骤S3中，低含水量的料浆含水量控制在25%～30%。
与现有技术相比，本发明优势在于：
1、本发明以氧化锆球为球磨介质进行湿式球磨，不会带入新的杂质，从而影响配方的准确性；以葡萄糖酸钙和异丁烯-马来酸酐共聚物的混合物为分散剂，可以提高料浆的取向度；
2、本发明以低含量的La-Co取代为主配方设计，通过合适的工艺，引入多元微量添加剂，制备出高性能的永磁铁氧体；生产出来的产品具有较高的磁性能，剩磁Br≥4300Gs、磁感矫顽力Hcb≥3900Oe、内禀矫顽力Hcj≥4100Oe、磁能积BH≥4.2MGOe，达到日本TDK公司FB6B牌号指标要求。
具体实施方式
下面将对本发明实施例中的技术方案进行详细的描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例；基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
以下，我们将采用本技术方案制备的永磁铁氧体与樟脑作为粘结剂生产的永磁铁氧体进行性能对比：
实施例1
S1制备预烧料：按配方LaxSr1-xO·n[（Fe1-yCoy）2O3]称取SrCO3、La2O3、Co2O3和Fe2O3，其中n=5.95、x=0.15、y=0.09，混合原料后，以氧化锆球为球磨介质进行湿式球磨，球磨料浆粒度控制在≤7.50μm，将球磨料浆烘干后，置于预烧料窑炉内烧结，预烧温度控制在1280℃；预烧保温时间控制在2.2h。得到预烧料；
S2 掺杂添加剂：添加所述预烧料重量0.9％的CaCO3、0.5％的Cr2O3、0.3％的Bi2O3、0.15％的Al2O3、0.45％的H3BO3作为添加剂，添加所述预烧料重量0.23％的葡萄糖酸钙和0.18％的异丁烯-马来酸酐共聚物作为分散剂；
S3 球磨制备料浆：将步骤S2所得物料以氧化锆球为球磨介质进行湿式球磨，球磨后料浆粒度控制在≤0.72μm，将球磨后料浆脱水得28%含水量的料浆；
S4 压制成型：采用湿式成型液压机压制样品，压制压强100MPa，取向磁场10000Oe，得到生坯；
S5 烧结：将步骤S4中制备的生坯放在推板窑上烧结，烧结温度1220℃，保温时间100 min；
S6 后处理：将步骤S5烧结出来的生坯磨削、清洗、检测，得到产品。
实施例2
S1制备预烧料：按配方LaxSr1-xO·n[（Fe1-yCoy）2O3]称取SrCO3、La2O3、Co2O3和Fe2O3，其中n=6.00、x=0.13、y=0.11，混合原料后，以氧化锆球为球磨介质进行湿式球磨，球磨料浆粒度控制在≤7.0μm，将球磨料浆烘干后，置于预烧料窑炉内烧结，预烧温度控制在1260℃；预烧保温时间控制在2.4h，得到预烧料；
S2 掺杂添加剂：添加所述预烧料重量0.8％的CaCO3、0.4％的Cr2O3、0.4％的Bi2O3、0.2％的Al2O3、0.5％的H3BO3作为添加剂，添加所述预烧料重量0.26％的葡萄糖酸钙和0.16％的异丁烯-马来酸酐共聚物作为分散剂；
S3 球磨制备料浆：将步骤S2所得物料以氧化锆球为球磨介质进行湿式球磨，球磨后料浆粒度控制在≤0.68μm，将球磨后料浆脱水得26%含水量的料浆；
S4 压制成型：采用湿式成型液压机压制样品，压制压强100MPa，取向磁场10000Oe，得到生坯；
S5 烧结：将步骤S4中制备的生坯放在推板窑上烧结，烧结温度1230℃，保温时间90 min；
S6 后处理：将步骤S5烧结出来的生坯磨削、清洗、检测，得到产品。
实施例3
S1制备预烧料：按配方LaxSr1-xO·n[（Fe1-yCoy）2O3]称取SrCO3、La2O3、Co2O3和Fe2O3，其中n=6.05、x=0.11、y=0.13，混合原料后，以氧化锆球为球磨介质进行湿式球磨，球磨料浆粒度控制在≤6.0μm，将球磨料浆烘干后，置于预烧料窑炉内烧结，预烧温度控制在1240℃；预烧保温时间控制在2.6h。得到预烧料；
S2 掺杂添加剂：添加所述预烧料重量0.7％的CaCO3、0.3％的Cr2O3、0.5％的Bi2O3、0.25％的Al2O3、0.55％的H3BO3作为添加剂，添加所述预烧料重量0.29％的葡萄糖酸钙和0.12％的异丁烯-马来酸酐共聚物作为分散剂；
S3 球磨制备料浆：将步骤S2所得物料以氧化锆球为球磨介质进行湿式球磨，球磨后料浆粒度控制在≤0.70μm，将球磨后料浆脱水得28%含水量的料浆；
S4 压制成型：采用湿式成型液压机压制样品，压制压强100MPa，取向磁场10000Oe，得到生坯；
S5 烧结：将步骤S4中制备的生坯放在推板窑上烧结，烧结温度1240℃，保温时间80 min；
S6 后处理：将步骤S5烧结出来的生坯磨削、清洗、检测，得到产品。
将上述实施例1-3产品进行测试，测试方法为：产品的剩磁Br、磁感矫顽力Hcb、内禀矫顽力Hcj 、磁能积BH，采用中国计量科学研究院生产的NIM-500C永磁高温测量仪测量，可输出J-H 回线、B-H 回线、退磁曲线等，测试环境温度为25℃左右，测试结果的重复性为：Br、Hcb、Hcj 均为±0.2%。
采用上述测试方法分别对本实施例1-3产品进行磁性能测试，结果列于下表中：
由表中可以看出，本实施例1-3产品在磁性能方面，产品的剩磁Br、磁感矫顽力Hcb、内禀矫顽力Hcj 、磁能积(BH)max，达到日本TDK公司FB6B牌号的指标要求。
上述实施例仅为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围；凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (4)

1.一种高性能永磁铁氧体的制备方法，其特征在于，依次包括如下步骤：
S1制备预烧料：按配方LaxSr1-xO·n[（Fe1-yCoy）2O3]称取碳酸锶SrCO3、氧化镧La2O3、氧化钴Co2O3和氧化铁Fe2O3，其中n=5.9~6.1、x=0.10~0.15、y=0.08~0.13，混合原料后，以氧化锆球为球磨介质进行湿式球磨，将球磨料浆烘干后，置于预烧料窑炉内烧结，得到预烧料；
S2掺杂添加剂：添加所述预烧料重量0.8~0.9％的CaCO3、0.4~0.5％的Cr2O3、0.3~0.5％的Bi2O3、0.15~0.25％的Al2O3、0.45~0.55％的H3BO3作为添加剂，添加所述预烧料重量0.23~0.29％的葡萄糖酸钙和0.12~0.18％的异丁烯-马来酸酐共聚物作为分散剂；
S3球磨制备料浆：将步骤S2所得物料以氧化锆球为球磨介质进行湿式球磨，将球磨后料浆脱水得低含水量的料浆；
S4压制成型：采用湿式成型液压机压制样品，压制压强≥100MPa，取向磁场≥8000Oe，得到生坯；
S5烧结：将步骤S4中制备的生坯放在推板窑上烧结，烧结温度1200~1260℃，保温时间80~100min；
S6后处理：将步骤S5烧结出来的生坯磨削、清洗、检测，得到产品。
2.根据权利要求1所述的高性能永磁铁氧体的制备方法，其特征在于，步骤S1中，球磨料浆粒度控制在≤8μm；预烧温度控制在1200~1300℃；预烧保温时间控制在2~3h。
3.根据权利要求1所述的高性能永磁铁氧体的制备方法，其特征在于，步骤S3中，球磨后料浆粒度控制在≤0.75μm。
4.根据权利要求1所述的高性能永磁铁氧体的制备方法，其特征在于，步骤S3中，低含水量的料浆含水量控制在25%~30%。
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