CN111180160A - 还原扩散各向同性钐铁氮粉末及磁体的工艺 - Google Patents
还原扩散各向同性钐铁氮粉末及磁体的工艺 Download PDFInfo
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- 239000011575 calcium Substances 0.000 claims abstract description 37
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
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- 230000009467 reduction Effects 0.000 claims abstract description 26
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000009792 diffusion process Methods 0.000 claims abstract description 24
- 238000005121 nitriding Methods 0.000 claims abstract description 24
- 229910001954 samarium oxide Inorganic materials 0.000 claims abstract description 23
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- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 21
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- 239000007789 gas Substances 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003822 epoxy resin Substances 0.000 claims abstract description 7
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- 238000002156 mixing Methods 0.000 claims abstract description 6
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- 238000003801 milling Methods 0.000 claims abstract description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000292 calcium oxide Substances 0.000 claims description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
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- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 3
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- 238000003723 Smelting Methods 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
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- 238000012544 monitoring process Methods 0.000 description 2
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- AWWAHRLLQMQIOC-UHFFFAOYSA-N [Fe].[Sm] Chemical compound [Fe].[Sm] AWWAHRLLQMQIOC-UHFFFAOYSA-N 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
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- 230000004584 weight gain Effects 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种还原扩散各向同性钐铁氮粉末及磁体的工艺，包括如下步骤：(1)、原料的重量配比为：氧化钐200‑300克，铁粉600‑700克，还原剂60‑100克，采用钙或氢化钙或钙/乙烷作为还原剂，用V型混料机混25‑35分种；(2)、进行还原扩散反应，反应温度为1180‑1200℃，时间为1‑5小时；(3)、还原扩散反应后物料进行破碎；(4)、氮化：氮化反应在氮气或氮氢混合气体或氮气乙烷混合气体中进行，氮化温度采用500‑600℃，氮化时间采用1‑5小时；(5)、环氧树脂粘结磁体，磨粉时间设定在2分钟。本发明的有益效果为：本发明还原扩散工艺，原料用氧化钐不用金属钐，省去从氧化钐到金属钐的提纯工艺节省了成本。
Description
技术领域
本发明涉及钐铁氮领域，主要是一种还原扩散各向同性钐铁氮粉末及磁体的工艺。
背景技术
钐铁氮研究已有很常的历史，压制环氧树脂粘结钐铁氮磁体最大磁能比压制环氧树脂粘结快淬钕铁硼磁体最大磁能高40％。目前我国钐铁氮粉末制备都用快淬工艺，由于熔融态钐金属蒸汽压很高，烧损量大，熔炼母合金加快淬钐烧损量高达5wt％，不但增加原料费用，而且成分控制困难，成分偏差导致氮化工艺波动和性能不稳。所以至今我国无规模化钐铁氮粉末和磁体生产先例。
发明内容
本发明的目的在于克服现有技术存在的不足，而提供一种还原扩散各向同性钐铁氮粉末及磁体的工艺。
本发明的目的是通过如下技术方案来完成的。一种还原扩散各向同性钐铁氮粉末及磁体的工艺，包括如下步骤：
(1)、原料的重量配比为：氧化钐200-300克，铁粉600-700克，还原剂60-100克，采用钙或氢化钙或钙/乙烷作为还原剂，用V型混料机混25-35分种；
(2)、进行还原扩散反应，反应温度为1180-1200℃，时间为1-5小时；
(3)、还原扩散反应后物料进行破碎；
(4)、氮化：氮化反应在氮气或氮氢混合气体或氮气乙烷混合气体中进行，氮化温度采用500-600℃，氮化时间采用1-5小时；
(5)、环氧树脂粘结磁体，磨粉时间设定在2分钟。
更进一步的，在步骤(3)中，还原扩散反应后物料进行破碎，用抽滤瓶和酒精喷壶冲洗粉末，当氧化钙、氧化钙和碳粉冲洗干净后，用乙酸冲洗清除残余在粉末颗粒夹缝内的残余氧化钙痕迹，通过化学分析粉末中的残余钙含量监控氧化钙分离是否彻底，控制标准为钙含量<0.1wt％。
更进一步的，在步骤(4)中，氮化反应后使得粉末的氮含量达到2.8。
更进一步的，在步骤(1)中，原料的重量配比为：氧化钐245.9克，669.33克，84.77克。
本发明的有益效果为：本发明还原扩散工艺，原料用氧化钐不用金属钐，省去从氧化钐到金属钐的提纯工艺节省了成本；用钙或氢化钙或钙/乙烷作为还原剂，还原扩散后能快速冷却，可减小粉末晶粒尺寸，从而使粉末氮化反应更容易。氮化反应在氮气或氮氢混合气体或氮气乙烷混合气体中进行，氮氢混合气体中的氢起到还原作用，因而可增加Sm2Fel7粉末活性，加速氮化反应过程，乙烷气体中含有氢离子，比游离氢分子更有利于Sm2Fel7粉末氮化。限定了氮含量2.8的粉末比氮含量1.9的粉末温度稳定性好。
具体实施方式
下面将结合实施例对本发明做详细的介绍：
本发明公开了一种还原扩散各向同性钐铁氮粉末及磁体的工艺，包括如下步骤：
(1)、原料的重量配比为：氧化钐200-300克，铁粉600-700克，还原剂60-100克，采用钙或氢化钙或钙/乙烷作为还原剂，用V型混料机混25-35分种；
(2)、进行还原扩散反应，反应温度为1180-1200℃，时间为1-5小时；
(3)、还原扩散反应后物料进行破碎；用抽滤瓶和酒精喷壶冲洗粉末，当氧化钙、氧化钙和碳粉冲洗干净后，用乙酸冲洗清除残余在粉末颗粒夹缝内的残余氧化钙痕迹，通过化学分析粉末中的残余钙含量监控氧化钙分离是否彻底，控制标准为钙含量<0.1wt％。
(4)、氮化：氮化反应在氮气或氮氢混合气体或氮气乙烷混合气体中进行，氮化温度采用500-600℃，氮化时间采用1-5小时；氮化反应后使得粉末的氮含量达到2.8。实验：两种氮含量粉末饱和磁化强度的温度依赖性，经检测氮含量2.8的粉末比氮含量1.9的粉末温度稳定性好。氮化反应前后需要精确称量物料增重，以确定钐铁氮粉末中氮含量是多少。
(5)、环氧树脂粘结磁体，磨粉时间设定在2分钟。实验：环氧树脂粘结磁体磁性与磨粉时间的关系，通过实验可知矫顽力随磨粉时间延长单调上升，Br和密度随磨粉时间延长而下降，磁能随磨粉时间变化出现峰值，峰值出现在磨2分钟时。
本发明还原扩散工艺，原料用氧化钐不用金属钐，省去从氧化钐到金属钐的提纯工艺节省了成本。2019年11月25日网上氧化钐价格为12.5元/公斤，金属钐价格为200元/公斤，后者是前者的16倍。
Sm2Fe17合金粉末钙热还原扩散用Ca或CaH2或Ca/乙烷为还原剂，反应温度和时间分别为1180-1200℃ X 1-5小时，反应方程如下：
用Ca作为还原剂方程式：
1180-1200℃X1-5hrs
Sm2O3+17Fe+3Ca＝Sm2Fe17+3CaO
用CaH2作为还原剂方程式：
1180-1200℃X1-5hrs
Sm2O3+17Fe+3CaH2＝Sm2Fe17+3CaO+3H2
用Ca、C2H6作为还原剂方程式：
1180-1200℃X1-5hrs
Sm2O3+17Fe+3Ca+C2H6＝Sm2Fe17+3CaO+3H2+2C
如用Ca作还原剂，由于氧化钙化学自由能比氧化钐低，所以用钙或氢化钙或钙/乙烷作为还原剂，化学反应过程中钙和氧化钐中的氧化合，钐游离出来通过热扩散与铁形成Sm2Fe17型合金颗粒。由于还原扩散温度比传统熔炼合金的方法温度低，还原扩散反应时间比熔炼时间长，在1-5小时内完成，可以避免钐挥发。还原扩散后能快速冷却，可减小粉末晶粒尺寸，从而使最后一道工艺(粉末氮化)反应更容易。
如用CaH2或Ca/C2H6作还原剂时，由于氢和乙烷有还原作用，所以比Ca还原反应速度更快。还原扩散反应后物料呈松散块状，然后破碎至负80目粉末(氮化与粉末粒度的关系，可以看出粒度越小氮化越容易)，为避免破碎过程中粉末氧化，采用先抽真空后充氩气的破碎方法。破碎后的粉末含有氧化钙，用钙/乙烷作还原剂时破碎后的粉末含有少量碳粉，用无水酒精清除氧化钙和碳粉，为节省无水酒精和提高冲洗效率，用抽滤瓶和酒精喷壶冲洗粉末。当氧化钙和碳粉冲洗干净后，用乙酸冲洗清除残余在粉末颗粒夹缝内的残余氧化钙痕迹，这些残余氧化钙痕迹暴露在潮湿空气中时就吸水变为氢氧化钙，并伴随体积膨胀，会使这种粉末制备的粘结磁体粉化。通过化学分析粉末中的残余钙含量监控氧化钙分离是否彻底，控制标准为<0.1wt％。
粉末氮化是影响钐铁氮材料性能的关键环节，氮化必须充分，氮化不充分磁性下降，化学稳定性和磁稳定性都会下降。氮化反应在氮气或氮氢混合气体或氮气乙烷混合气体中进行，氮氢混合气体中的氢起到还原作用，因而可增加Sm2Fel7粉末活性，加速氮化反应过程。乙烷气体中含有氢离子，比游离氢分子更有利于Sm2Fel7粉末氮化。氮化温度采用550℃，氮化时间采用1-5小时，温度过高氮化物会分解，吸氮发生在500℃到600℃温度范围，温度再高开始放氮，加铌后放氮温度升高，并且放氮速度变慢。钐铁粉末在500℃，550℃和600℃三个温度的氮化行为，可见600℃时小于等于38μ的粉末半小时不到就氮化完毕。
实施例1-3：原料的重量配比为：氧化钐200克，铁粉600克，还原剂60克；分别采用钙或氢化钙或钙/乙烷作为还原剂。
实施例4-6：原料的重量配比为：氧化钐300克，铁粉700克，还原剂100克，分别采用钙或氢化钙或钙/乙烷作为还原剂。
实施例7：配料：氧化钐245.9克，铁粉669.33克，钙84.77克
用V型混料机混30分种还原扩散温度及时间：1200℃/2hs
除钙：抽滤瓶无水酒晶喷淋，加乙酸喷淋，加无水酒精喷淋，加抽滤干燥，用化学分析确认钙含量<0.1wt％
氮化：在氮氢混合气体中，温度600℃，时间4小时；
磁性能：环氧树脂粘结磁体(BH)max＝5.4MGOe,如果氮化不充分会导致磁性能偏低。
实施例8：配料：氧化钐245.9克，铁粉669.33克，钙84.77克
用V型混料机混30分种还原扩散还原扩散温度及时间：1200℃/2hs
除钙：抽滤瓶无水酒晶喷淋，加乙酸喷淋，加无水酒精喷淋，加抽滤干燥，用化学分析确认钙含量<0.1wt％
氮化：乙烷气体，温度600℃，时间4小时
磁性能：环氧树脂粘结磁体(BH)max＝13.8MGOe，性能改善的原因是乙烷气体氮化效率比氮气氮化效率明显高。
以下三个表格分别示出了钐铁氮塑料粘结磁体性能，钐铁氮粉末可用作制备压制环氧树脂粘结磁体或注射塑料粘结磁体，与钕铁硼粘结磁体比较钐铁氮粘结磁体的优点如下：
1，随温度的磁不可逆损失比钕铁硼低；
2，比钕铁硼容易磁化；
3，比重比钕铁硼约小30％，可减轻应用器件重量；
4，适用于对耐蚀性和温度稳定性有要求的汽车传感器和仪表；
5，各向同性钐铁氮可在磁性橡皮方面取代钕铁硼和铁氧体；
6，由于粉末颗粒形状不同，压制环形钐铁氮粘结磁体有比钕铁硼粘结磁体小的尺寸公差；
7，压制磁体有比钕铁硼高的强度和高的温度稳定性(低Br温度系数和低不可逆损失，有利于传感器应用)；
8，有比钕铁硼高的耐蚀性。
钐铁氮和钕铁硼环氧粘结和塑料粘结剩磁温度系数对比，和两种材料环氧粘结磁体抗弯强度比较。
钐铁氮环氧树脂粘结磁体抗弯强度比钕铁硼高。
可以理解的是，对本领域技术人员来说，对本发明的技术方案及发明构思加以等同替换或改变都应属于本发明所附的权利要求的保护范围。
Claims (4)
1.一种还原扩散各向同性钐铁氮粉末及磁体的工艺，其特征在于：包括如下步骤：
(1)、原料的重量配比为：氧化钐200-300克，铁粉600-700克，还原剂60-100克，采用钙或氢化钙或钙/乙烷作为还原剂，用V型混料机混25-35分种；
(2)、进行还原扩散反应，反应温度为1180-1200℃，时间为1-5小时；
(3)、还原扩散反应后物料进行破碎；
(4)、氮化：氮化反应在氮气或氮氢混合气体或氮气乙烷混合气体中进行，氮化温度采用500-600℃，氮化时间采用1-5小时；
(5)、环氧树脂粘结磁体，磨粉时间设定在2分钟。
2.根据权利要求1所述的还原扩散各向同性钐铁氮粉末及磁体的工艺，其特征在于：在步骤(3)中，还原扩散反应后物料进行破碎，用抽滤瓶和酒精喷壶冲洗粉末，当氧化钙、氧化钙和碳粉冲洗干净后，用乙酸冲洗清除残余在粉末颗粒夹缝内的残余氧化钙痕迹，通过化学分析粉末中的残余钙含量监控氧化钙分离是否彻底，控制标准为钙含量<0.1wt％。
3.根据权利要求1所述的还原扩散各向同性钐铁氮粉末及磁体的工艺，其特征在于：在步骤(4)中，氮化反应后使得粉末的氮含量达到2.8。
4.根据权利要求1所述的还原扩散各向同性钐铁氮粉末及磁体的工艺，其特征在于：在步骤(1)中，原料的重量配比为：氧化钐245.9克，669.33克，84.77克。
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