CN114566370A - 低温氧化/氮化处理提高钕铁硼抗蚀性的方法 - Google Patents
低温氧化/氮化处理提高钕铁硼抗蚀性的方法 Download PDFInfo
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- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 28
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 23
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- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 150000004767 nitrides Chemical class 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
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- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
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- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
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- 239000011780 sodium chloride Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052779 Neodymium Inorganic materials 0.000 description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 5
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 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
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- C21D8/1255—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest with diffusion of elements, e.g. decarburising, nitriding
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- 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
本发明公开一种低温氧化/氮化处理提高钕铁硼抗蚀性的方法，通过200～400℃的低温氧化/氮化处理，在钕铁硼磁体表面原位生长氧化物、氮化物或氮氧化物薄层，大幅提高磁体的抗蚀性。本方法操作简单，生产成本低，不同于传统电镀和化学镀等方法，是一种绿色、安全、高效的技术方法。根据工艺调整，磁体表面生成的氧化物、氮化物或氮氧化物薄层厚度在10nm～100μm间连续可调，提高磁体抗蚀性的同时可保持优异的磁性能。并且，本方法磁体表面薄层为原位生成，与基体结合力强，长时稳定，可大批量推广应用。
Description
技术领域
本发明涉及腐蚀防护领域，具体涉及低温氧化/氮化处理提高钕铁硼抗蚀性的方法。
背景技术
钕铁硼永磁材料具有高矫顽力、高剩磁、高磁能积等优异的综合磁性能，是应用最广泛的稀土永磁材料，已发展成为新能源、轨道交通、电子信息和航天航空等国民经济和国防建设的关键基础材料之一。尽管钕铁硼磁性很强，其极易腐蚀的缺陷严重影响了在海上风电、国防军工等重要领域的应用。已经发现，钕铁硼低抗蚀性的主要原因是晶界富钕相的电极电位太低，优先氧化腐蚀和吸氢粉化，形成晶间腐蚀并导致铁磁性Nd2Fe14B主相晶粒脱落，最终导致磁体磁性失效。
为了提高钕铁硼的抗蚀性，过去研究人员主要关注合金成分和表面防护两方面的研究。由于需要保持Nd2Fe14B主相的晶体结构以保障优异的磁性能，通过调整钕铁硼合金成分提高抗蚀性的作用十分有限。表面防护需要对钕铁硼磁体进行复杂的多次电镀、化学镀或电泳处理等，不仅提高了生产成本，易引起各种环保问题，而且由于钕铁硼基体与镀层结合力较差，镀层在磁体服役过程中易于剥落，降低了可靠性。因此，如何提高钕铁硼磁体的抗蚀性，一直是稀土永磁材料行业的难点。
发明内容
本发明的目的是克服现有技术的不足，提供一种低温氧化/氮化处理提高钕铁硼抗蚀性的方法。
本发明使用低温氧化/氮化处理方法，在钕铁硼磁体表面原位生长氧化物、氮化物或氮氧化物薄层，大幅提高磁体的抗蚀性。其特征在于：在管式炉或气氛炉中，抽真空至10-2～10-4Pa后，通入气体，气体为O2、N2、NH3或水蒸气中的一种或几种，流量为15～5000ml/min，低温氧化或氮化的温度控制在200～400℃，反应时间控制在0.5～24h。
所述氧化物、所述氮化物或所述氮氧化物的薄层厚度在10nm～100μm间连续可调。
所述钕铁硼磁体的成分，以原子百分数计，为(REaRE’1-a)x(FebM1-b)100-x-y-zM’yBz，RE为除La、Ce、Y以外的其它镧系元素中的一种或几种，RE’为La、Ce、Y元素中的一种或几种；Fe为铁元素，M为Co或Ni中的一种或两种；M’为Nb、Zr、Ta、V、Al、Cu、Ga、Ti、Cr、Mo、Mn、Ag、Au、Pb、Si元素中的一种或几种，B为硼元素；a、b、x、y、z满足以下关系：0.55≤a≤1、0.8≤b≤1、12≤x≤18、0≤y≤2、5.5≤z≤6.5。
本发明与现有技术相比的有益效果：1)传统方法是基于长期以来对低电位富钕相的认识，通过合金化微调富钕相的成分，提高其电极电位，降低其与主相电位差；或通过磁体表面镀Cu、镀Ni等保护涂层，隔绝富Nd相与腐蚀液的直接接触；不同于这些传统方法，本发明的最大创新在于充分利用了富钕相中稀土元素含量高，易于氧化或氮化的特征，经低温氧化/氮化处理，在钕铁硼磁体表面形成一层高电位的氧化物、氮化物或氮氧化物薄层，具有良好的化学稳定性和致密性，大幅提高磁体的腐蚀电位，降低腐蚀电流，可起到表面防护的效果；2)针对不同成分的钕铁硼磁体，其高丰度稀土La、Ce、Y含量不同，Fe、Co、Ni含量不同，合金化元素含量不同等，导致磁体富钕相的成分、结构、含量和分布均不同，通过针对性调整氧化/氮化工艺参数，均可大幅提升磁体的抗蚀性；3)磁体表面原位生长的氧化物、氮化物或氮氧化物薄层厚度在10nm～100μm间连续可调，相对于不同尺寸的磁体(mm级的薄片磁体到≥10cm级的大块磁体)，均可在提高抗蚀性的同时，保持磁体优异的磁性能；4)原位生长的氧化物、氮化物或氮氧化物薄层与钕铁硼基体的结合力较强，可提高工作寿命；5)相较于钕铁硼的传统真空或惰性气体保护高温热处理(450～1050℃)，本发明仅需一步低温氧化/氮化气氛处理(200～400℃)，工艺流程简单，成本较低；6)氧化/氮化处理后的钕铁硼磁体可免于后续电镀、化学镀等镀层处理，可减少环境污染。
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：
钕铁硼磁体的成分，以原子百分数计，为(Pr0.2Nd0.8)14Fe78.95(Cu0.5Al0.2Ga0.2Zr0.1)1B6.05，在管式炉中抽真空至2×10-2Pa后，通入O2，流量为800ml/min，低温氧化的温度控制在350℃，反应时间控制在3h。磁体表面原位生成的氧化物薄层厚度为～1μm。AMT-4永磁特性测量仪测试结果显示，表面氧化处理后磁体的剩磁为14.0kG，矫顽力为14.8kOe。AMETEK电化学工作站测试结果显示，在3.5％NaCl溶液中，表面氧化处理后磁体的腐蚀电流为5μA/cm2。
对比例1：
与实施例1的不同之处在于，磁体未经低温氧化处理。AMT-4永磁特性测量仪测试结果显示，磁体的剩磁为14.0kG，矫顽力为14.9kOe，均与实施例1相近。AMETEK电化学工作站测试结果显示，在3.5％NaCl溶液中，磁体的腐蚀电流为70μA/cm2，较实施例1增大了一个数量级以上。
对比例2：
与实施例1的不同之处在于，提高Cu元素含量，磁体的成分，以原子百分数计，为(Pr0.2Nd0.8)14Fe77.95(Cu1.5Al0.2Ga0.2Zr0.1)1B6.05，且未经低温氧化处理。AMT-4永磁特性测量仪测试结果显示，磁体的剩磁为13.6kG，矫顽力为11.7kOe，较实施例1均大幅下降。AMETEK电化学工作站测试结果显示，在3.5％NaCl溶液中，磁体的腐蚀电流为52μA/cm2，较实施例1增大了一个数量级以上。
对比例3：
与实施例1的不同之处在于，磁体未经低温氧化处理，经表面镀层处理，为亮银色镍铜镍镀层，镀层厚度～10μm。AMT-4永磁特性测量仪测试结果显示，磁体的剩磁为13.7kG，矫顽力为14.2kOe，较实施例1均下降。AMETEK电化学工作站测试结果显示，在3.5％NaCl溶液中，磁体的腐蚀电流为10μA/cm2，大于实施例1。
实施例2：
钕铁硼磁体的成分，以原子百分数计，为[Nd0.65(La0.35Ce0.65)0.35]16(Fe0.97Co0.03)76.15(Ga0.35Cu0.2Al0.2Nb0.1Zr0.05)2B5.85，在管式炉中抽真空至3×10-3Pa后，通入O2，流量为200ml/min，低温氧化的温度控制在300℃，反应时间控制在0.5h。磁体表面原位生成的氧化物薄层厚度为～200nm。AMT-4永磁特性测量仪测试结果显示，表面氧化处理后磁体的剩磁为12.4kG，矫顽力为11.1kOe。AMETEK电化学工作站测试结果显示，在3.5％NaCl溶液中，表面氧化处理后磁体的腐蚀电压为-430mV。
对比例4：
与实施例2的不同之处在于，磁体未经低温氧化处理。AMT-4永磁特性测量仪测试结果显示，磁体的剩磁为12.4kG，矫顽力为11.2kOe，均与实施例2相近。AMETEK电化学工作站测试结果显示，在3.5％NaCl溶液中，磁体的腐蚀电压为-870mV，较实施例2明显降低。
实施例3：
钕铁硼磁体的成分，以原子百分数计，为(Pr0.2Nd0.8)18Fe75.55(Ga0.7Al0.15Zr0.15)0.55B5.9，在气氛炉中抽真空至2×10-4Pa后，通入NH3，流量为80ml/min，低温氮化的温度控制在400℃，反应时间控制在1h。磁体表面原位生成的氮化物薄层厚度为～300nm。AMT-4永磁特性测量仪测试结果显示，表面氮化处理后磁体的剩磁为13.6kG，矫顽力为17.5kOe。AMETEK电化学工作站测试结果显示，在3.5％NaCl溶液中，表面氮化处理后磁体的腐蚀电流为11μA/cm2。
对比例5：
与实施例3的不同之处在于，磁体未经低温氮化处理。AMT-4永磁特性测量仪测试结果显示，磁体的剩磁为13.5kG，矫顽力为17.4kOe，均与实施例3相近。AMETEK电化学工作站测试结果显示，在3.5％NaCl溶液中，磁体的腐蚀电流为317μA/cm2，较实施例3增大了一个数量级以上。
实施例4：
钕铁硼磁体的成分，以原子百分数计，为[(Pr0.1Nd0.9)0.75(Y0.15Ce0.85)0.25]15(Fe0.9Co0.1)77.4(Cu0.3Ga0.15Al0.25Si0.2Nb0.1)1.5B6.1，在管式炉中抽真空至1×10-3Pa后，通入O2和N2混合气，比例为7:3，流量为500ml/min，低温氧化和氮化的温度控制在350℃，反应时间控制在12h。磁体表面原位生成的氮氧化物薄层厚度为～5μm。AMT-4永磁特性测量仪测试结果显示，表面氧化和氮化处理后磁体的剩磁为12.6kG，矫顽力为13.0kOe。AMETEK电化学工作站测试结果显示，在3.5％NaCl溶液中，表面氧化和氮化处理后磁体的腐蚀电压为-240mV。
对比例6：
与实施例4的不同之处在于，未经低温氧化和氮化处理。AMT-4永磁特性测量仪测试结果显示，磁体的剩磁为12.6kG，矫顽力为13.3kOe，均与实施例4相近。AMETEK电化学工作站测试结果显示，在3.5％NaCl溶液中，磁体的腐蚀电压为-730mV，较实施例4明显降低。
Claims (4)
1.低温氧化/氮化处理提高钕铁硼抗蚀性的方法，其特征在于：通过低温氧化/氮化处理，在钕铁硼磁体表面原位生长氧化物、氮化物或氮氧化物薄层。
2.根据权利要求1所述的方法，其特征在于：在管式炉或气氛炉中，抽真空至10-2～10- 4Pa后，通入气体，气体为O2、N2、NH3或水蒸气中的一种或几种，流量为15～5000ml/min，低温氧化/氮化的温度控制在200～400℃，反应时间控制在0.5～24h。
3.根据权利要求1所述的方法，其特征在于：所述氧化物、所述氮化物或所述氮氧化物的薄层厚度在10nm～100μm间连续可调。
4.根据权利要求1所述的方法，其特征在于：所述钕铁硼磁体的成分，以原子百分数计，为(REaRE’1-a)x(FebM1-b)100-x-y-zM’yBz，RE为除La、Ce、Y以外的其它镧系元素中的一种或几种，RE’为La、Ce、Y元素中的一种或几种；Fe为铁元素，M为Co或Ni中的一种或两种；M’为Nb、Zr、Ta、V、Al、Cu、Ga、Ti、Cr、Mo、Mn、Ag、Au、Pb、Si元素中的一种或几种，B为硼元素；a、b、x、y、z满足以下关系：0.55≤a≤1、0.8≤b≤1、12≤x≤18、0≤y≤2、5.5≤z≤6.5。
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