WO2019047295A1 - 一种成分和粒度可调控的钐钴化合物纳米颗粒的制备方法 - Google Patents

一种成分和粒度可调控的钐钴化合物纳米颗粒的制备方法 Download PDF

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WO2019047295A1
WO2019047295A1 PCT/CN2017/104333 CN2017104333W WO2019047295A1 WO 2019047295 A1 WO2019047295 A1 WO 2019047295A1 CN 2017104333 W CN2017104333 W CN 2017104333W WO 2019047295 A1 WO2019047295 A1 WO 2019047295A1
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particle size
cobalt compound
nanoparticles
purity
samarium
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岳明
吴琼
刘卫强
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Beijing University of Technology
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    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

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  • the invention relates to a method for preparing a samarium cobalt compound nanoparticle by evaporation condensation using a samarium cobalt alloy, and belongs to the technical field of nanometer permanent magnet material preparation.
  • Samarium-cobalt permanent magnet is the first generation of rare earth permanent magnet alloy developed in the 1960s. It not only has excellent intrinsic magnetic properties, but also has good high temperature performance. Therefore, it still has high practical value, and the temperature requirement is higher. Under the high use environment, it plays an irreplaceable role. At present, samarium-cobalt-based permanent magnet materials are widely used in many national defense and high-tech fields such as aerospace, nuclear energy technology and electric vehicles.
  • the recently developed surfactant-assisted ball milling method of samarium cobalt nanoparticles introduces an organic surfactant that is difficult to remove, resulting in a significant decrease in particle oxidation and magnetic properties. Therefore, it is extremely urgent to develop a new technology capable of mass-producing high-performance samarium cobalt nanoparticles.
  • the invention adopts a samarium-cobalt alloy prepared by smelting of elemental bismuth and cobalt metal as raw materials, and successfully prepares Sm 2 Co 7 and SmCo 5 by in-situ generation and in-situ collection under inert gas-protected anaerobic conditions.
  • the present invention provides a method for preparing samarium cobalt compound nanoparticles using an inert gas evaporation condensation technique in situ.
  • the objective is to obtain samarium cobalt compound nanoparticles having an average particle diameter of less than 100 nm and uniform particle size.
  • the specific process includes the following samarium cobalt alloy smelting and evaporation condensation steps:
  • Sm x Co 100-x mother alloy obtained in the step 1) is used as an anode, the metal tungsten is used as a cathode, and the purity is 99.9999% argon gas, the purity is 99.9999% helium gas or a mixed atmosphere of the two. (The ratio between the two is arbitrarily adjustable from 0 to 100%), the total pressure is 1 atmosphere, the arc current is 100-300A, the arc voltage is 20-40V, and the arcing time is 0.1-1 hour.
  • Sm x Co 100-x The master alloy was prepared as SmCo nanoparticles, and the particles were collected through an atmosphere-protected sealed can.
  • the samarium cobalt nanoparticle provided by the invention has uniformity and the average particle diameter is less than or equal to 100 nm.
  • a plurality of samarium cobalt nanoparticles having different chemical compositions, crystal structures and magnetic properties can be obtained.
  • the average particle size of the produced samarium cobalt nanoparticles can be controlled, and the prepared nanoparticles have a good particle size distribution, that is, the particle size uniformity is good.
  • the whole process maintains high purity inert gas protection, avoids oxidation, and the comprehensive magnetic properties of the product are good.
  • Figures 1-2 and Table 1 show the results of the microstructure (represented by SmCo 5 nanoparticles) and magnetic properties of the prepared samarium cobalt nanoparticles.
  • the Sm 24 Co 76 master alloy is used as the anode and the metal tungsten is used as the cathode.
  • the nanoparticles are prepared by evaporation condensation under the protection of a helium atmosphere with a purity of 99.9999%.
  • the arc current is 100A
  • the arc voltage is 20V
  • the arc is started.
  • the time is 0.1 hours.
  • Sm 2 Co 7 nanoparticles having an average particle diameter of 30 nm were prepared, and the particles were collected by an atmosphere-protected sealed can.
  • Table 1 Main magnetic properties of SmCo magnets prepared in Examples 1-4: saturation magnetization, residual magnetization, coercivity and magnetic energy product

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  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

一种成分和粒度可调控的钐钴化合物纳米颗粒的制备方法，属于纳米永磁材料制备技术领域。采用单质钐和钴金属熔炼制备的钐钴合金为原料，在高纯度惰性气体保护的无氧条件下，以原位生成、原位收集的蒸发冷凝的方式制备出Sm 2Co 7、SmCo 5、SmCo 7、Sm 2Co 17等多种平均粒径小于100纳米且粒度可控的钐钴化合物纳米颗粒。这种方法工艺简单，生产周期短，同时全过程保持高纯度惰性气体保护，避免氧化，产品的综合磁性能良好。

Description

一种成分和粒度可调控的钐钴化合物纳米颗粒的制备方法 技术领域
本发明涉及一种利用钐钴合金通过蒸发冷凝制备钐钴化合物纳米颗粒的制备方法的方法，属于纳米永磁材料制备技术领域。
背景技术
钐钴永磁体，是上世纪60年代开发的第一代稀土永磁合金，不仅具有优异的内禀磁性能，而且具有良好的高温性能，因此至今仍有较高的实用价值，在温度要求较高的使用环境下发挥着不可替代的作用，目前钐钴基永磁材料在航空航天、核能技术、电动汽车等诸多国防和高技术领域应用广泛。
近年来，纳米材料因为其独特的性能而广受关注。常规材料在实现纳米化以后会具有许多新的性能，因而具有更好的潜在应用价值。钐钴化合物纳米颗粒在磁存储、生物医用和新型复合永磁等方面均具有良好的应用前景。遗憾的是，目前制备钐钴纳米颗粒的方法及其制备出的材料均存在较多问题。例如目前较为流行的化学合成法，只能研制出具有纳米晶的微米级钐钴颗粒，而且产量极低，无法实现大规模制造。又如近期发展的表面活性剂辅助球磨法制备的钐钴纳米颗粒会引入难以去除的有机表面活性剂，造成颗粒氧化和磁性能大幅下降。因此，发展一种能够批量制造高性能钐钴纳米颗粒的新技术迫在眉睫。
针对这种状况，我们发明了一种以钐钴合金为原料，通过惰性气体保护的蒸发冷凝技术制备成分和粒度可调控的钐钴化合 物纳米颗粒的方法，以期推动高性能钐钴纳米颗粒永磁材料的实用化进程。
发明内容
本发明以采用单质钐和钴金属熔炼制备的钐钴合金为原料，在惰性气体保护的无氧条件下，以原位生成、原位收集的方式成功的制备出Sm2Co7、SmCo5、SmCo7、Sm2Co17等多种粒度可控的钐钴化合物纳米颗粒。
本发明提供一种利用原位的惰性气体蒸发冷凝技术制备钐钴化合物纳米颗粒的方法。目的在于获得平均粒径小于100纳米且颗粒度均匀的钐钴化合物纳米颗粒。具体过程包括如下的钐钴合金熔炼和蒸发冷凝步骤：
1)选用纯度大于99.99％的Sm和Co金属单质原料，按照SmxCo100-x中元素摩尔比准备原料，然后在纯度为99.9999％的氩气气氛保护下的悬浮熔炼炉中熔炼得到SmxCo100-x母合金，0＜x≤24；
2)以步骤1)得到的SmxCo100-x母合金中的任何一种作为阳极，金属钨作为阴极，在纯度为99.9999％的氩气、纯度为99.9999％氦气或者二者的混合气氛(二者比例在0～100％间任意可调)下，总气压为1个大气压，选择电弧电流100—300A，电弧电压20—40V，起弧时间0.1－1小时将SmxCo100-x母合金制备成SmCo纳米颗粒，并将颗粒通过气氛保护密封罐进行收集。
本发明提供的钐钴纳米颗粒度均匀，平均粒径小于等于100 纳米，通过调控母合金的成分，可以获得具有不同化学成分、晶体结构和磁性能的多种钐钴纳米颗粒。通过调节蒸发冷凝过程的各项工艺参数可以实现对生产钐钴纳米颗粒平均粒径的调控，而且所制备的纳米颗粒具有较好的粒度分布，即粒度均匀性较好。同时全过程保持高纯度惰性气体保护，避免氧化，产品的综合磁性能良好。附图1-2和表1给出了所制备钐钴纳米颗粒的微结构(以SmCo5纳米颗粒为代表)和磁性能的结果。
附图说明
图1是本发明所制备的SmCo5纳米颗粒的微观形貌和晶体结构(透射电子显微镜照片和选区电子衍射图片)。
图2是本发明所制备的SmCo5纳米颗粒的磁滞回线图。
具体实施方式
下面结合实施例对本发明作进一步说明，但本发明并不限于以下实施例。
实施例1：
1)选用纯度大于99.99％的Sm和Co金属原料，按照24:76摩尔比的成分配比，在纯度为99.999％的氩气气氛保护下的悬浮熔炼炉中熔炼得到Sm24Co76母合金。
2)将Sm24Co76母合金作为阳极，金属钨作为阴极，在纯度为99.9999％的氦气气氛保护下通过蒸发冷凝的方法制备纳米颗粒，反应中采用电弧电流100A，电弧电压20V，起弧时间0.1小时。制备出平均粒径30纳米的Sm2Co7纳米颗粒，并将颗粒通过 气氛保护密封罐进行收集。
实施例2：
1)选用纯度大于99.99％的Sm和Co金属原料，按照18:82的摩尔比成分配比，在纯度为99.999％的氩气气氛保护下的悬浮熔炼炉中熔炼得到Sm18Co82母合金。
2)将Sm24Co76母合金作为阳极，金属钨作为阴极，在纯度为99.9999％的氦氩混合气氛(氦气：氩气＝30：70)保护下通过蒸发冷凝的方法制备纳米颗粒，反应中采用电弧电流150A，电弧电压25V，起弧时间0.3小时。制备出SmCo5纳米颗粒，并将颗粒通过气氛保护密封罐进行收集。所得到的平均粒径50纳米的SmCo5纳米颗粒的微观形貌和晶体结构如图1所示，磁滞回线如图2所示。
实施例3：
1)选用纯度大于99.99％的Sm和Co金属原料，按照14:86的摩尔比成分配比，在纯度为99.999％的氩气气氛保护下的悬浮熔炼炉中熔炼得到Sm14Co86母合金。
2)将Sm14Co86母合金作为阳极，金属钨作为阴极，在纯度为99.9999％的氦氩混合气氛(氦气：氩气＝70：30)保护下通过蒸发冷凝的方法制备纳米颗粒，反应中采用电弧电流250A，电弧电压30V，起弧时间0.8小时。制备出平均粒径80纳米的SmCo7纳米颗粒，并将颗粒通过气氛保护密封罐进行收集。
实施例4：
1)选用纯度大于99.99％的Sm和Co金属原料，按照12:88的成分配比，在纯度为99.999％的氩气气氛保护下的悬浮熔炼炉中熔炼得到Sm12Co88母合金。
2)将Sm14Co86母合金作为阳极，金属钨作为阴极，在纯度为99.9999％的氩气气氛保护下通过蒸发冷凝的方法制备纳米颗粒，反应中采用电弧电流300A，电弧电压40V，起弧时间1小时。制备出平均粒径100纳米的Sm2Co17纳米颗粒，并将颗粒通过气氛保护密封罐进行收集。
表1实施例1-4中制备的SmCo磁体的主要磁性能参数：饱和磁化强度、剩余磁化强度、矫顽力和磁能积
Figure PCTCN2017104333-appb-000001

Claims (2)

  1. 一种成分和粒度可调控的钐钴化合物纳米颗粒的制备方法，其特征在于，包括以下步骤：
    1)选用纯度大于99.99％的Sm和Co金属单质原料，按照SmxCo100-x中元素摩尔比准备原料，然后在纯度为99.9999％的氩气气氛保护下的悬浮熔炼炉中熔炼得到SmxCo100-x母合金，0＜x≤24；
    2)以步骤1)得到的SmxCo100-x母合金中的任何一种作为阳极，金属钨作为阴极，在纯度为99.9999％的氩气、纯度为99.9999％氦气或者二者的混合气氛(二者比例在0～100％间任意可调)下，总气压为1个大气压，选择电弧电流100—300A，电弧电压20—40V，起弧时间0.1－1小时将SmxCo100-x母合金制备成SmCo纳米颗粒，并将颗粒通过气氛保护密封罐进行收集。
  2. 按照权利要求1所述的一种成分和粒度可调控的钐钴化合物纳米颗粒的制备方法，其特征在于，钐钴化合物纳米颗粒平均粒径小于等于100纳米。
PCT/CN2017/104333 2017-09-07 2017-09-29 一种成分和粒度可调控的钐钴化合物纳米颗粒的制备方法 Ceased WO2019047295A1 (zh)

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