CN111063536B - 一种适用于大块稀土永磁材料的晶界扩散方法 - Google Patents
一种适用于大块稀土永磁材料的晶界扩散方法 Download PDFInfo
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- 238000005324 grain boundary diffusion Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 28
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title claims abstract description 9
- 238000009792 diffusion process Methods 0.000 claims abstract description 18
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 15
- 239000000956 alloy Substances 0.000 claims abstract description 15
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- 238000004026 adhesive bonding Methods 0.000 claims abstract description 6
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 3
- 238000009713 electroplating Methods 0.000 claims abstract description 3
- 238000007731 hot pressing Methods 0.000 claims abstract description 3
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 239000000865 liniment Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 2
- 229910052779 Neodymium Inorganic materials 0.000 claims 1
- 229910052777 Praseodymium Inorganic materials 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000002490 spark plasma sintering Methods 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000696 magnetic material Substances 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 4
- 229910001172 neodymium magnet Inorganic materials 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种适用于大块稀土永磁材料的晶界扩散方法。本发明使用放电等离子烧结技术对磁体进行晶界扩散处理，改善磁体的综合磁性能。包括以下步骤：(1)通过烧结或热压或热变形工艺制备得到初始磁体；(2)通过磁控溅射、电镀、化学气相沉积、物理气相沉积、直接物理接触或粘结剂粘结的方法在磁体表面负载晶界扩散合金源；(3)将负载后的初始磁体放入放电等离子装置中，使用放电等离子加热升温进行晶界扩散，得到最终磁体。通过控制放电等离子烧结过程中电流、等离子及压力等，显著提高元素的扩散系数，增强元素的扩散深度。本发明制备的晶界扩散的稀土永磁材料，磁性能增幅更显著，且能使晶界扩散工艺适用于大块磁体，不受磁体厚度的限制，满足工业生产及市场需求。
Description
技术领域
本发明本涉及永磁领域，具体来说，涉及一种适用于大块稀土永磁材料的晶界扩散方法。
背景技术
钕铁硼具有优异的综合磁性能，广泛应用于能源、信息、交通和国防等领域，是最重要的稀土功能材料和国民经济的关键基础材料之一。然而烧结钕铁硼的温度稳定性差，工作温度通常低于100℃，电动汽车、风电及航空航天等应用大幅受限。目前，使用廉价的高丰度稀土La/Ce/Y，取代价格昂贵的Nd/Pr/Dy/Tb，大幅降低稀土永磁的原材料成本，获得了国内外广泛关注。然而，镧铈钇形成的2:14:1相的内禀磁性弱于钕铁硼，富高丰度稀土永磁的磁稀释显著，尤其是矫顽力低，无法满足商用要求。该问题难以解决，长期制约了高丰度稀土永磁的发展和应用。
目前，提高钕铁硼矫顽力的方法主要包括：1)熔炼添加重稀土，但在主相中大量引入均匀分布的Dy/Tb，不仅消耗稀缺重稀土资源，极大提高原材料成本，而且大幅降低剩磁和磁能积；2)晶粒细化，但磁粉粒径下降后易氧化，晶粒降至3μm以下时，矫顽力反而降低；3)晶界扩散，可大幅提高磁体矫顽力，且操作简单，可大幅提高稀土的利用效率。因此，晶界扩散是目前的研究热点。然而受限于元素扩散深度的限制，普通晶界扩散工艺仅适用于厚度小于5mm的磁体，因此规模化应用受限。如何提高晶界扩散深度，实现一种适用于大块稀土永磁材料的晶界扩散方法，是目前稀土永磁领域的研究难点。
发明内容
本发明的目的是克服现有技术的不足，提供了一种适用于大块稀土永磁材料的晶界扩散方法，包括以下步骤：
(1)通过烧结或热压或热变形工艺制备得到初始磁体；
(2)在初始磁体表面负载晶界扩散合金源；
(3)将负载后的初始磁体放入放电等离子装置中，使用放电等离子加热升温进行晶界扩散，升温速度为20～400℃/min，扩散温度400～900℃，施加压力2～50MPa，保温时间20～180min，真空度不低于10-3Pa，得到最终磁体。
步骤(3)中制备的最终磁体，以质量百分数计，其成分为：(RxA1-x)yQbalMzBw，R为高丰度稀土La、Ce、Y元素中的一种或几种，A为除La、Ce、Y外的其他镧系稀土元素中的一种或几种，Q为Fe、Co、Ni元素中的一种或几种，M为Al、Cr、Cu、Zn、Ga、Ge、Mn、Mo、Nb、P、Pb、Si、Ta、Ti、V、Zr、O、F、N、C、S、H元素中的一种或几种，B为硼元素；x、y、z、w满足以下关系：0≤x≤0.8，26≤y≤36，1≤z≤10，0.8≤w≤1.3。
步骤(1)中的初始磁体，以质量百分数计，其成分为：(R’aA’1-a)bQ’balM’cBd，R’为高丰度稀土La、Ce、Y元素中的一种或几种，A’为除La、Ce、Y外的其他镧系稀土元素中的一种或几种，Q’为Fe、Co、Ni元素中的一种或几种，M’为Al、Cr、Cu、Zn、Ga、Ge、Mn、Mo、Nb、P、Pb、Si、Ta、Ti、V、Zr、O、F、N、C、S、H元素中的一种或几种，B为硼元素；a、b、c、d满足以下关系：0≤a≤0.8，23≤b≤33，0.5≤c≤8，0.9≤d≤1.4。
步骤(2)中的晶界扩散合金源，以质量百分数计，其成分为：R”uM”1-u，R”为镧系稀土元素中的一种或几种，M”为Fe、Co、Ni、Al、Cr、Cu、Zn、Ga、Ge、Mn、Mo、Si、Ti、O、F、H元素中的一种或几种，u满足以下关系：0≤u≤1。
步骤(2)中负载晶界扩散合金源的方式包括：磁控溅射、电镀、化学气相沉积、物理气相沉积、直接物理接触、粘接剂粘结。
本发明与现有技术相比具有的有益效果：
1)本发明基于放电等离子烧结技术进行晶界扩散。加热过程中，由于电流、等离子及压力的影响，能够提高元素的扩散系数，磁体内出现扩散的高速通道，加速稀土及合金元素进入磁体内部(晶界或晶粒内部)，从而增强元素的扩散深度，磁性能显著提高，成为一种适用于大块稀土永磁材料的晶界扩散方法，La、Ce、Y取代量最高达80％。
2)本发明利用放电等离子烧结技术升温速度快，加热时间短的特点，大幅抑制扩散过程中的晶粒长大，进一步提高磁体的矫顽力。
具体实施方式
下面结合具体实施例对本发明做进一步说明，但本发明并不仅仅局限于以下实施例：
实施例1：
通过烧结工艺制备得到高度为25mm的初始磁体(Pr0.12Nd0.48Ce0.4)30.8FebalCu0.3Al0.2Ga0.2Zr0.3B1.05；晶界扩散合金粉末Nd80Al20通过直接接触的方式负载在初始磁体表面后，放入放电等离子装置中，升温速度为400℃/min，扩散温度700℃，施加压力20MPa，保温时间40min，得到最终磁体，磁性能为Br＝12.4kG，Hcj＝15.5kOe，(BH)max＝36.6MGOe。
实施例2：
通过烧结工艺制备得到高度为20mm的初始磁体(Nd0.4La0.2Ce0.4)32FebalNb0.3Ti0.2Ga0.5Co0.3B0.9；晶界扩散合金粉末NdH3通过PVP粘接剂粘结的方式负载在初始磁体表面后，放入放电等离子装置中，升温速度为20℃/min，扩散温度900℃，施加压力50MPa，保温时间100min，得到最终磁体，磁性能为Br＝12.2kG，Hcj＝12.5kOe，(BH)max＝33.4MGOe。
实施例3：
通过热变形工艺制备得到高度为10mm的初始磁体(Nd0.5Y0.1Ce0.4)30FebalZr0.15Cu0. 3Co0.5Al0.2B1.01；晶界扩散合金粉末Nd70Cu30通过PVP粘接剂粘结的方式负载在初始磁体表面后，放入放电等离子装置中，升温速度为400℃/min，扩散温度600℃，施加压力2MPa，保温时间60min，得到最终磁体，磁性能为Br＝11.3kG，Hcj＝16.5kOe，(BH)max＝28.2MGOe。
实施例4：
通过烧结工艺制备得到高度为18mm的初始磁体(Pr0.18Nd0.72Ce0.1)36FebalMo0.15Al0.15Cu0.2Zr0.2B0.95；晶界扩散合金源Dy20Pr60Al20通过磁控溅射的方式负载在初始磁体表面后，放入放电等离子装置中，升温速度为400℃/min，扩散温度800℃，施加压力25MPa，保温时间180min，得到最终磁体，磁性能为Br＝12.5kG，Hcj＝25.4kOe，(BH)max＝39.2MGOe。
实施例5：
通过热变形工艺制备得到高度为8mm的初始磁体(Nd0.2Ce0.8)26FebalZr0.1Cu0.2Co0.5Al0.3Si0.1B1.0；晶界扩散合金粉末Pr70Cu30通过磁控溅射的方式负载在初始磁体表面后，放入放电等离子装置中，升温速度为100℃/min，扩散温度650℃，施加压力5MPa，保温时间20min，得到最终磁体，磁性能为Br＝10.1kG，Hcj＝11.2kOe，(BH)max＝20.3MGOe。
Claims (4)
1.一种适用于大块稀土永磁材料的晶界扩散方法，其特征在于，包括以下步骤：
(1)通过烧结或热压或热变形工艺制备得到初始磁体，其成分为：(R’aA’1-a)bQ’balM’cBd，R’为高丰度稀土La、Ce、Y元素中的一种或几种，A’为除La、Ce、Y外的其他镧系稀土元素中的一种或几种，Q’为Fe、Co、Ni元素中的一种或几种，M’为Al、Cr、Cu、Zn、Ga、Ge、Mn、Mo、Nb、P、Pb、Si、Ta、Ti、V、Zr、O、F、N、C、S、H元素中的一种或几种，B为硼元素；a、b、c、d满足以下关系：0<a≤0.8，23≤b≤33，0.5≤c≤8，0.9≤d≤1.4；
(2)在初始磁体表面负载晶界扩散合金源，其成分为：R”uM”1-u，R”为Nd、Pr轻稀土元素中的一种或两种，M”为Fe、Co、Ni、Al、Cr、Cu、Zn、Ga、Ge、Mn、Mo、Si、Ti、O、F、H元素中的一种或几种，u满足以下关系：0<u<1；
(3)将负载后的初始磁体放入放电等离子装置中，使用放电等离子加热升温进行晶界扩散，升温速度为20～400℃/min，扩散温度400～900℃，施加压力2～50MPa，保温时间20～180min，真空度小于10-3Pa，得到最终磁体。
2.根据权利要求1所述的方法，其特征在于，步骤(2)中负载晶界扩散合金源的方式包括：磁控溅射、电镀、化学气相沉积、物理气相沉积、直接物理接触或粘接剂粘结。
3.根据权利要求1所述的方法，其特征在于，通过烧结工艺制备得到高度为25mm的初始磁体(Pr0.12Nd0.48Ce0.4)30.8FebalCu0.3Al0.2Ga0.2Zr0.3B1.05；晶界扩散合金粉末Nd0.8Al0.2通过直接接触的方式负载在初始磁体表面后，放入放电等离子装置中，升温速度为400℃/min，扩散温度700℃，施加压力20MPa，保温时间40min，得到最终磁体。
4.根据权利要求1所述的方法，其特征在于，通过烧结工艺制备得到高度为20mm的初始磁体(Nd0.4La0.2Ce0.4)32FebalNb0.3Ti0.2Ga0.5Co0.3B0.9；晶界扩散合金粉末Nd0.25H0.75通过PVP粘接剂粘结的方式负载在初始磁体表面后，放入放电等离子装置中，升温速度为20℃/min，扩散温度900℃，施加压力50MPa，保温时间100min，得到最终磁体。
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