CN108515177A - 一种具有多主相结构的纳米晶复合稀土永磁材料及其制备 - Google Patents
一种具有多主相结构的纳米晶复合稀土永磁材料及其制备 Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 34
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 31
- 239000000696 magnetic material Substances 0.000 title claims abstract description 18
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 79
- 239000000843 powder Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000006247 magnetic powder Substances 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 8
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims description 16
- 230000007704 transition Effects 0.000 claims description 12
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 10
- 229910052779 Neodymium Inorganic materials 0.000 claims description 9
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 18
- 239000000956 alloy Substances 0.000 abstract description 18
- 238000002156 mixing Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 239000000155 melt Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 40
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 229910001172 neodymium magnet Inorganic materials 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 238000010891 electric arc Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000007578 melt-quenching technique Methods 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
本发明公开了一种具有多主相结构的纳米晶复合稀土永磁材料及其制备方法，将CexFe101‑x‑y‑zByMz磁粉与(PraNd1‑a)bFe100‑b‑c‑dBcMd粉末按质量比为20‑80：20‑80均匀混合，通过放电等离子烧结技术制备得到具有多主相结构的纳米晶复合永磁材料，其中：CexFe101‑x‑y‑zByMz磁粉，其中M为Cu、Al、Ga、Nb、Zr、Hf元素中的一种或多种，11≤x≤20，3≤y≤10，0≤z≤3；(PraNd1‑a)bFe100‑b‑c‑dBcMd磁粉，其中M为Cu、Al、Ga、Nb、Zr、Hf元素中的一种或多种，0≤a≤1，10≤b≤20，3≤c≤10，0≤d≤3。本发明利用具有硬磁性能的快淬合金粉末，改善了永磁体的微观结构、磁性能和耐腐蚀性能，充分利用了高丰度稀土元素Ce，得到了具有多主相结构的纳米晶复合永磁材料。此外，本发明还具有烧结时间短，工艺流程简单的特点，有效促进了稀土资源的高效平衡利用。
Description
技术领域
本发明属于稀土永磁材料领域，特别提供一种具有多主相结构的纳米晶复合稀土永磁材料及其制备方法。
背景技术
Nd2Fe14B类稀土永磁材料由于其优异的磁性能，被广泛的应用于风力发电、消费类电子、医疗器械、新能源汽车、航空航天、轨道交通等领域。钕铁硼(Nd-Fe-B)磁体的广泛应用促使全球对中低丰度稀土元素钕、镨、镝、铽的需求猛增。钕铁硼磁体中稀土金属含量约为31wt.％，伴随着钕铁硼市场的高速增长，全球对钕铁硼的主要原料稀土金属钕、镨、镝、铽的需求也在强劲增长。稀土需求量的猛增导致了关键稀土元素价格的大幅波动，对钕铁硼制造企业和下游应用产业造成巨大压力。一方面，Nd-Fe-B基永磁材料强烈依赖于Nd、Pr和Dy等贵重稀土资源，其中Nd、Pr使用量占据稀土总量的70wt.％以上，消耗巨大；另一方面，以Ce为主的高丰度稀土元素在稀土永磁中未获得大量应用，长期处于供过于求的市场积压状态，造成稀土资源的严重不平衡利用。
纳米晶磁体所特有的微观结构特点及较强的晶间交换耦合作用，使得其温度稳定性和断裂韧性要好于传统烧结磁体和粘结磁体。一般而言，多主相结构磁体具有比单主相结构磁体更优异的磁性能。因此，具有多主相结构的含Ce磁体的开发可充分利用高丰度稀土Ce，降低磁体成本，提高永磁体性价比，也可实现稀土资源的高效平衡利用。
发明内容
本发明的目的在于充分利用高丰度稀土Ce，并通过双合金技术，获得纳米晶复合磁体的多主相结构，从而进一步提高磁体磁性能。
本发明技术方案如下：
一种具有多主相结构的纳米晶复合稀土永磁材料，其特征在于：将具有硬磁性能的CexFe101-x-y-zByMz磁粉与(PraNd1-a)bFe100-b-c-dBcMd粉末按质量比为20-80：20-80均匀混合，通过放电等离子烧结技术制备得到具有多主相结构的纳米晶复合稀土永磁材料，其中：
CexFe101-x-y-zByMz磁粉，其中M为Cu、Al、Ga、Nb、Zr、Hf元素中的一种或多种，11≤x≤20，3≤y≤10，0≤z≤3；
(PraNd1-a)bFe100-b-c-dBcMd磁粉，其中M为Cu、Al、Ga、Nb、Zr、Hf元素中的一种或多种，0≤a≤1，10≤b≤20，3≤c≤10，0≤d≤3。
其中：CexFe101-x-y-zByMz磁粉中部分Fe元素可由Co替代；(PraNd1-a)bFe100-b-c-dBcMd磁粉中部分Fe元素可由Co替代，部分Pr、Nd元素可由Dy、Tb、Ho、Gd中的一种或多种替代。
本发明还提供了所述多主相结构的纳米晶复合稀土永磁材料的制备方法，其特征在于：通过放电等离子烧结技术制备所述纳米晶复合稀土永磁材料，放电等离子烧结前及整个烧结过程真空度小于10Pa，烧结温度为600～850℃，烧结压力为20～100MPa，烧结时间为0～20min。
制备所得磁体中存在三个居里温度转变点，即磁体中存在三主相，通过改变两种粉末的质量百分比，可以实现调控磁体居里温度的目的。同时，所得磁体中主相晶粒尺寸在纳米级别。
本发明所述多主相结构的纳米晶复合稀土永磁材料的制备方法，其特征在于，具体步骤如下：
①、将元素Ce、Fe、B、M按照CexFe101-x-y-zByMz配比，成分中部分Fe元素也可由Co元素取代；将配好的原材料放入电弧炉中，在氩气气氛下进行熔炼得到母合金铸锭，并通过熔体快淬的方式制备得到快淬合金带材，在气氛保护下将合金带破碎成粉末；
②、将元素Pr、Nd、Fe、B、M按照(PraNd1-a)bFe100-b-c-dBcMd配比，成分中部分Pr、Nd元素可由Dy、Tb、Ho、Gd替代，部分Fe元素可由Co替代；将配好的原材料放入电弧炉中，在氩气气氛下进行熔炼得到母合金铸锭，并通过熔体快淬的方式制备得到快淬合金带材，在气氛保护下将合金带破碎成粉末；
③、将CexFe101-x-y-zByMz粉末和(PraNd1-a)bFe100-b-cBcMd粉末按质量比为20-80：20-80均匀混合，倒入石墨模具中，通过放电等离子烧结设备制成具有双主相结构的纳米晶磁体。烧结温度为600～850℃，烧结压力为20～100MPa，烧结时间为0～20min。
一般而言，双主相结构磁体是利用两种具有硬磁性能的粉料获得，本发明通过两种具有硬磁性能的粉料混合，采用放电等离子快速烧结技术制备得到了纳米晶型三主相复合永磁体。磁体中同时存在三个不同成分的RE2Fe14B主相，通过控制低熔点稀土合金的添加种类和添加量，实现磁体居里转变点的可控调整，且各居里温度之间差别较大。本发明具有烧结时间短，工艺流程简单的特点，有效促进了稀土资源的高效平衡利用。
附图说明
图1为纳米晶复合永磁体M-T曲线。
图2为纳米晶复合永磁体透射电镜形貌图。
具体实施方式
以下结合附图实施例对本发明作进一步详细描述，但本发明不限于这些实施例，以下实施例只为说明目的，不应当被用来限制本发明以及权利要求的范围。
实施例1
将元素Ce、Fe、B、Nb、Cu、Ga、Co按照Ce17Fe74.5Co2B6Nb0.5Cu0.5Ga0.5配比，将配好的原材料放入电弧炉中，在氩气气氛下进行熔炼得到母合金铸锭，通过甩带机制备得到快淬合金带材，其中辊速为19m/s，在氩气保护下将合金带破碎成粉末；将元素Pr、Nd、Fe、B、Hf按照(Pr0.2Nd0.8)13Fe80.5B6Hf0.5配比，将配好的原材料放入电弧炉中，在氩气气氛下进行熔炼得到母合金铸锭，并通过熔体快淬的方式制备得到快淬合金带材，其中甩带机辊速为18m/s，在氩气保护下将合金带破碎成粉末；在氩气保护下将Ce17Fe74.5Co2B6Nb0.5Cu0.5Ga0.5粉末和(Pr0.2Nd0.8)13Fe80.5B6Hf0.5粉末按质量比80：20均匀混合。将混合粉末倒入石墨模具中，通过放电等离子烧结设备快速烧结制得磁体。烧结前及整个烧结过程真空度小于10Pa，烧结温度为660℃，烧结压力为50MPa，烧结时间为5min。
图1为磁体M-T曲线。从图中可以看出，磁体中存在三个居里转变点，分别为Tc1＝441K，Tc2＝493K，Tc3＝580K，表明磁体中存在三个硬磁主相，具有三主相结构。图2为磁体内部透射电镜形貌图。可以看出，磁体晶粒尺寸在纳米级别。
对比例1
将元素Ce、Fe、B、Nb、Cu、Ga、Co按照Ce17Fe74.5Co2B6Nb0.5Cu0.5Ga0.5配比，将配好的原材料放入电弧炉中，在氩气气氛下进行熔炼得到母合金铸锭，通过甩带机制备得到快淬合金带材，其中辊速为19m/s，在氩气保护下将合金带破碎成粉末；将Ce17Fe74.5Co2B6Nb0.5Cu0.5Ga0.5粉末倒入石墨模具中，通过放电等离子烧结设备快速烧结制得磁体。放电等离子烧结前及整个烧结过程真空度小于10Pa，烧结温度为650℃，烧结压力为50MPa，烧结时间为2min。
磁体中存在1个居里转变点，为Tc＝443K，表明磁体中仅存在着一个主相。
对比例2
将元素Pr、Nd、Fe、B、Hf按照(Pr0.2Nd0.8)13Fe80.5B6Hf0.5配比，将配好的原材料放入电弧炉中，在氩气气氛下进行熔炼得到母合金铸锭，通过甩带机制备得到快淬合金带材，其中辊速为18m/s，在氩气保护下将合金带破碎成粉末；将(Pr0.2Nd0.8)13Fe80.5B6Hf0.5粉末倒入石墨模具中，通过放电等离子烧结设备快速烧结制得磁体。烧结前及整个烧结过程真空度小于10Pa，烧结温度为700℃，烧结压力为50MPa，烧结时间为5min。
磁体中存在1个居里转变点，为Tc＝581K，表明磁体中仅存在着一个主相。
实施例2
与实施例1的不同之处在于：将Ce17Fe74.5Co2B6Nb0.5Cu0.5Ga0.5粉末和(Pr0.2Nd0.8)13Fe80.5B6Hf0.5粉末按质量比60：40均匀混合。将混合粉末倒入石墨模具中，通过放电等离子烧结设备快速烧结制得磁体。放电等离子烧结前及整个烧结过程真空度小于10Pa，烧结温度为670℃，烧结压力为50MPa，烧结时间为5min。
磁体中存在三个居里转变点，分别为Tc1＝446K，Tc2＝505K，Tc3＝577K，表明磁体中存在三个硬磁主相，具有三主相结构。
实施例3
与实施例1的不同之处在于：将Ce17Fe74.5Co2B6Nb0.5Cu0.5Ga0.5粉末和(Pr0.2Nd0.8)13Fe80.5B6Hf0.5粉末按质量比40：60均匀混合。将混合粉末倒入石墨模具中，通过放电等离子烧结设备快速烧结制得磁体。放电等离子烧结前及整个烧结过程真空度小于10Pa，烧结温度为680℃，烧结压力为60MPa，烧结时间为3min。
磁体中存在三个居里转变点，分别为Tc1＝447K，Tc2＝516K，Tc3＝575K，表明磁体中存在三个硬磁主相，具有三主相结构。
实施例4
与实施例1的不同之处在于：将Ce17Fe74.5Co2B6Nb0.5Cu0.5Ga0.5粉末和(Pr0.2Nd0.8)13Fe80.5B6Hf0.5粉末按质量比20：80均匀混合。将混合粉末倒入石墨模具中，通过放电等离子烧结设备快速烧结制得磁体。放电等离子烧结前及整个烧结过程真空度小于10Pa，烧结温度为690℃，烧结压力为70MPa，烧结时间为6min。
磁体中存在三个居里转变点，分别为Tc1＝452K，Tc2＝515K，Tc3＝578K，表明磁体中存在三个硬磁主相，具有三主相结构。
实施例5
将Ce15Fe78.5B6Nb1.0Ga0.5粉末和(Pr0.2Nd0.8)15Fe79B6粉末按质量比75：25均匀混合。将混合粉末倒入石墨模具中，通过放电等离子烧结设备快速烧结制得磁体。放电等离子烧结前及整个烧结过程真空度小于10Pa，烧结温度为700℃，烧结压力为60MPa，烧结时间为6min。
磁体中存在三个居里转变点，表明磁体中存在三个硬磁主相，具有三主相结构。
实施例6
将Ce14Fe78B6Zr1.5Ga1.5粉末和(Pr0.2Nd0.8)13Fe77.5Co3B6Cu0.5粉末按质量比60：40均匀混合。将混合粉末倒入石墨模具中，通过放电等离子烧结设备快速烧结制得磁体。放电等离子烧结前及整个烧结过程真空度小于10Pa，烧结温度为720℃，烧结压力为50MPa，烧结时间为8min。
磁体中存在三个居里转变点，也具有三主相结构。
实施例7
将Ce19Fe74.5B6Nb1.5粉末和(Pr0.2Nd0.8)13Fe80.5B6Hf0.5粉末按质量比50：50均匀混合。将混合粉末倒入石墨模具中，通过放电等离子烧结设备快速烧结制得磁体。放电等离子烧结前及整个烧结过程真空度小于10Pa，烧结温度为750℃，烧结压力为50MPa，烧结时间为6min。
磁体中存在三个居里转变点，也具有三主相结构。
上述实施例只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 (6)
1.一种具有多主相结构的纳米晶复合稀土永磁材料，其特征在于：将CexFe101-x-y-zByMz磁粉与(PraNd1-a)bFe100-b-c-dBcMd粉末按质量比为20-80：20-80均匀混合，通过放电等离子烧结技术制备得到具有多主相结构的纳米晶复合稀土永磁材料，其中：
CexFe101-x-y-zByMz磁粉，其中M为Cu、Al、Ga、Nb、Zr、Hf元素中的一种或多种，11≤x≤20，3≤y≤10，0≤z≤3；
(PraNd1-a)bFe100-b-c-dBcMd磁粉，其中M为Cu、Al、Ga、Nb、Zr、Hf元素中的一种或多种，0≤a≤1，10≤b≤20，3≤c≤10，0≤d≤3。
2.按照权利要求1所述多主相结构的纳米晶复合稀土永磁材料，其特征在于：CexFe101-x-y-zByMz磁粉中部分Fe元素由Co替代。
3.按照权利要求1所述多主相结构的纳米晶复合稀土永磁材料，其特征在于：(PraNd1-a)bFe100-b-c-dBcMd磁粉中部分Fe元素由Co替代，部分Pr、Nd元素由Dy、Tb、Ho、Gd中的一种或多种替代。
4.一种权利要求1所述多主相结构的纳米晶复合稀土永磁材料的制备方法，其特征在于：通过放电等离子烧结技术制备所述纳米晶复合稀土永磁材料，放电等离子放电等离子烧结前及整个烧结过程真空度小于10Pa，烧结温度为600～850℃，烧结压力为20～100MPa，烧结时间为0～20min。
5.按照权利要求4所述多主相结构的纳米晶复合稀土永磁材料的制备方法，其特征在于：所得磁体中存在三个居里温度转变点，通过改变两种粉末的质量百分比，可以实现调控磁体居里温度的目的。
6.按照权利要求4所述多主相结构的纳米晶复合稀土永磁材料的制备方法，其特征在于：所得磁体中主相晶粒尺寸在纳米级别。
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