CN111435630B - 软磁性材料的制造方法 - Google Patents

软磁性材料的制造方法 Download PDF

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CN111435630B
CN111435630B CN202010012394.8A CN202010012394A CN111435630B CN 111435630 B CN111435630 B CN 111435630B CN 202010012394 A CN202010012394 A CN 202010012394A CN 111435630 B CN111435630 B CN 111435630B
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CN111435630A (zh
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吉永文隆
芳贺一昭
宇都野正史
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Toyota Motor Corp
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Abstract

提供在软磁性合金基材上形成有由电阻率高的α‑Fe2O3单相构成的被膜的软磁性材料的制造方法。在包含水蒸气和惰性气体的气氛中加热软磁性合金基材，从而在所述软磁性合金基材上形成被膜。所述气氛的氧分压在0～1.5kPa的范围内。由此，制造出具备软磁性合金基材和形成于其表面的被膜的软磁性材料。

Description

软磁性材料的制造方法
技术领域
本发明涉及软磁性材料的制造方法。
背景技术
在电动机的铁心中作为软磁性材料使用电磁钢板。为了进一步提高能量转换效率，曾研究了作为软磁性材料使用合金薄带。为了防止合金薄带彼此的导通，合金薄带的表面需要由绝缘膜被覆。
在专利文献1中记载了如下内容：通过在包含水蒸气的氮气气氛下对软磁性合金薄带进行热处理，从而形成耐候性良好的被膜。在专利文献2中记载了在表面具有氧化被膜的软磁性合金薄带。另外，记载了：在软磁性合金薄带的制造方法中，在具有6～18％的氧浓度的气氛中对初期微结晶合金薄带进行热处理。在专利文献3中记载了如下内容：在不锈钢制太阳能电池用基板的制造方法中，通过在包含水蒸气的气氛中对不锈钢钢材进行热处理，从而在不锈钢钢材的表面形成绝缘性优异的氧化被膜。在专利文献4中记载了如下内容：将烧结钕磁铁在水蒸气气氛下加热至规定的温度，从而在烧结钕磁铁的表面形成包含Fe3O4和Fe2O3的氧化物层。
在先技术文献
专利文献
专利文献1：日本特开平05-082373号公报
专利文献2：日本特开2011-149045号公报
专利文献3：日本特开2014-218728号公报
专利文献4：日本特开2005-310975号公报
发明内容
希望电动机小型化，为此需要提高铁心的占空系数。但是，由于软磁性合金薄带的厚度小，因此为了提高占空系数，需要减小形成于表面的绝缘膜的厚度。为了维持绝缘性并且减小绝缘膜的厚度，需要更加提高绝缘膜的电阻率。
但是，本发明人深入研究的结果发现：利用专利文献1～4所记载的方法形成的被膜包含电阻率低的FeO和/或Fe3O4。
因此，本发明的目的是提供在软磁性合金基材上形成有由电阻率高的α-Fe2O3单相构成的被膜(α-Fe2O3单相膜)的软磁性材料的制造方法。
根据本发明的一个方式，提供一种软磁性材料的制造方法，该制造方法包括下述步骤：在包含水蒸气和惰性气体的气氛中加热软磁性合金基材，从而在上述软磁性合金基材上形成被膜，上述气氛的氧分压在0～1.5kPa的范围内。
采用本发明的制造方法制造的软磁性材料，具有由电阻率高的α-Fe2O3单相构成的被膜。因此，该软磁性材料能够实现由占空系数的提高带来的电动机的小型化和电动机的能量转换效率的提高。
附图说明
图1是实施例1的试样的XRD图谱。
图2是比较例1的试样的XRD图谱。
具体实施方式
对软磁性材料的制造方法的实施方式进行具体说明。
首先，准备软磁性合金基材。软磁性合金基材能够通过例如下述方法来得到：利用高频熔化炉等将以成为目标的组成的方式配合的金属原料在高温下熔融而形成为均匀的熔液，将其进行急冷。急冷后的软磁性合金基材也可以为非晶质。也可以进而将软磁性合金基材加热而使非晶质相结晶化而形成纳米晶。另外，也可以在用于后述的被膜形成的加热的期间使非晶质相结晶化而形成纳米晶。软磁性合金基材的形态不特别限定，可以为例如薄带、薄片、粒状物、块的形态，可以优选为薄带的形态。
软磁性合金基材为由Fe基合金构成的基材。“Fe基合金”是指包含Fe作为主成分的合金。在此，“包含Fe作为主成分”是指合金中的Fe的含量为50原子％以上。从采用实施方式的制造方法制造的软磁性材料具有高饱和磁化强度这样的观点出发，Fe基合金中的Fe的含量优选为80原子％以上，更优选为84原子％以上，进一步优选为88原子％以上。
Fe基合金除了Fe以外含有最低所需量的为了促进非晶质的形成而必需的元素(选自B、Si、P等中的至少1种半金属元素)。通过含有这样的元素，从熔液急冷后所得到的软磁性合金基材成为非晶质。
进而，Fe基合金也可以根据需要来含有元素M。M是选自Nb、Mo、Ta、W、Cu、Ni、Co和Sn中的至少1种金属。
在M为选自Nb、Mo、Ta、W和Sn中的至少1种金属的情况下，能抑制软磁性合金基材的由热处理所致的晶粒长大，能抑制矫顽力的增大，并且在热处理后残留的非晶质相稳定化。包含这些元素的Fe基合金，在热处理中的核生成频度高。在M为Cu的情况下，通过软磁性合金基材的热处理，引起以Cu团簇为起点的不均质核生成，形成微细的晶粒。即使Fe基合金中的Cu的含量极微少，晶粒的微细化效果也较大。但是，通过Fe基合金包含这些元素，Fe含量降低，因此饱和磁化强度降低。因此，Fe基合金中的这些元素的含量优选为所需最低限度。
另外，在M为Ni和Co的至少1种的情况下，能够控制感应磁各向异性的大小。另外，在M为Ni的情况下，能够使饱和磁化强度增大。
在Fe基合金含有M的情况下，相应于M的含量而发挥上述的作用。即，Nb、Mo、Ta、W和Sn发挥抑制晶粒长大和稳定非晶质相的作用，Cu发挥将晶粒微细化的作用，Ni和Co发挥控制感应磁各向异性的大小和增大饱和磁化强度的作用。
将准备的软磁性合金基材在包含水蒸气和惰性气体的气氛中加热。由此，在软磁性合金基材上形成被膜。作为惰性气体，可列举氮气、氩气、氦气等，但优选为氮气。气氛的露点可以为20～25℃。即，气氛中的水蒸气分压可以为2.3～3.2kPa。气氛中的氧分压为0～1.5kPa。通过在气氛中不包含氧气或者即使包含氧气也为1.5kPa以下的分压，从而通过加热而在软磁性合金基材的表面形成的被膜成为α-Fe2O3单相膜。另外，气氛中的氧分压也可以为0～0.1kPa。由此，能形成绝缘性更高的被膜。进而，从使被膜的绝缘性提高的观点出发，气氛中的氧分压可以为0～0.01kPa。气氛的总压可以为大气压。再者，即使将对软磁性合金基材进行加热的炉内通过用氮气进行置换等而形成为氮气气氛，通常炉内的氧分压也不会成为1.5kPa以下。通过将炉的抽真空(脱气)和氮气的导入反复进行多次，能够使炉内的氧分压成为0～1.5kPa、优选成为0～0.1kPa、特别地成为0～0.01kPa。
再者，软磁性合金基材的加热可以在实质上仅包含水蒸气和惰性气体的气氛中进行。在此，所谓“实质上仅包含水蒸气和惰性气体”，也包含以不对反应给予影响的程度的量含有水蒸气和惰性气体以外的成分的情况。
加热温度可以设为例如250～450℃。加热时间可以根据形成的被膜的厚度来适当设定。
通过以上所述，能得到具备软磁性合金基材和形成于其表面的被膜的软磁性材料。所形成的被膜为α-Fe2O3单相膜。所谓“α-Fe2O3单相膜”意指包含α-Fe2O3且实质上不包含其他的氧化铁相的膜。所谓“实质上不包含”意指不能够通过XRD等的设备分析来检测到。
在氧化铁中，除了α-Fe2O3相以外还有Fe3O4、FeO等的相。α-Fe2O3具有约106Ω·cm的高的电阻率。另一方面，Fe3O4和FeO的电阻率均为约10-3Ω·cm，比α-Fe2O3的电阻率低。如上述那样，采用实施方式的制造方法形成的被膜包含电阻率高的α-Fe2O3，实质上不包含电阻率低的Fe3O4、FeO等的氧化铁相，因此具有高的电阻率。因此，即使被膜的厚度小，被膜也能够具有高的绝缘性。因此，通过使用所制造的软磁性材料，能够形成占空系数高的铁心。
本发明人认为，采用本实施方式的制造方法能形成α-Fe2O3单相膜的原因是因为：通过气氛中的氧气含量少，经由氢氧化物而形成氧化铁。另外，本发明人认为：在气氛中的氧分压超过1.5kPa的情况下，在加热中来自软磁性合金基材的Fe的扩散速度和来自气氛的氧扩散速度产生差异，其结果，形成由Fe3O4、FeO等的氧化铁相构成的被膜。
所制造的软磁性材料能够作为电动机和电抗器(reactor)等的部件的铁心使用。
以上，对本发明的实施方式进行了详细叙述，但是，本发明并不被上述实施方式限定，能够在不脱离权利要求书所记载的本发明的精神的范围内进行各种设计变更。
实施例
以下，通过实施例和比较例来对本发明进行具体说明，但是，本发明并不被这些实施例限定。
实施例1
(1)软磁性合金基材的制作
以成为Fe84B12Ni3的组成的方式称量原材料(Fe、B和Ni)，并通过电弧熔化来熔化从而混合。为了均质地混合，一边使其翻转，一边反复进行4次的熔化。混合后，通过铸造而制作了合金的铸块。
将制作的合金的铸块切断以使得其能放入石英喷嘴(排出孔径Φ0.5mm)中。将切断了的铸块插入石英喷嘴内，设置于液体急冷装置(单辊法)，在惰性气氛中通过高频加热来熔化，得到熔液。然后，将熔液排出至圆周速度为60m/s的铜辊上，制作了宽度1mm、厚度13μm的软磁性合金薄带(软磁性合金基材)。石英喷嘴与铜辊的间隔设为0.4mm，熔液排出温度设为熔点+100℃，排出时的压差设为60kPa。
(2)被膜的形成
将制作的软磁性合金薄带设置于处理炉内。将炉内排气至5Pa后，用水蒸气和氮气的混合气体进行置换，用氧浓度计(日本ガイシ制SH-2D)测定了炉内的氧浓度。反复进行排气和置换直至氧浓度变为0.01％为止。炉内的总压设为大气压。接着，一边将炉内保持为大气压，一边流通水蒸气和氮气的混合气体，将软磁性合金薄带在300℃加热120分钟。加热中的氧浓度为0.01％，露点为24.1℃，均大致恒定。加热中的氮气、水蒸气和氧气的分压分别如表1所示。再者，水蒸气分压是按照JIS Z 8806求出的值。
(3)试样的评价
将所得到的试样的XRD图谱示于图1。观察到来自软磁性合金薄带的α-Fe的峰和来自形成于软磁性合金薄带上的被膜的α-Fe2O3的峰。没有观察到α-Fe2O3以外的相的氧化铁的峰。由此确认到由具有高的电阻率的α-Fe2O3单相构成的被膜的形成。
实施例2
反复进行处理炉的排气和置换直至氧浓度计显示0.1％为止，并且，将软磁性合金薄带在300℃加热180分钟，除此以外，与实施例1同样地制作了试样。再者，加热中的氧浓度为0.1％，露点为24.1℃，均大致恒定。加热中的氮气、水蒸气和氧气的分压分别如表1所示。由制作的试样的XRD图谱确认到形成了由α-Fe2O3单相构成的被膜。
实施例3
反复进行处理炉的排气和置换直至氧浓度计显示1％为止，并且，将软磁性合金薄带在400℃加热10分钟，除此以外，与实施例1同样地制作了试样。再者，加热中的氧浓度为1％，露点为24.1℃，均大致恒定。加热中的氮气、水蒸气和氧气的分压分别如表1所示。由制作的试样的XRD图谱确认到形成了由α-Fe2O3单相构成的被膜。
比较例1
不进行处理炉的排气和置换而在大气(空气)气氛中将软磁性合金薄带在450℃加热180分钟，除此以外，与实施例1同样地制作了试样。再者，加热中的氧浓度为18％，露点为14℃，均大致恒定。加热中的氮气、水蒸气和氧气的分压分别如表1所示。将制作的试样的XRD图谱示于图2。除了来自软磁性合金薄带的α-Fe的峰和来自形成于软磁性合金薄带上的氧化膜的α-Fe2O3的峰以外，也观察到FeO的峰。由此确认到形成了包含电阻率低的FeO相的被膜。
比较例2
将处理炉排气后用氧气进行了置换，并且，一边流通氧气一边将软磁性合金薄带在450℃加热180分钟，除此以外，与实施例1同样地制作了试样。再者，加热中的氮气、水蒸气和氧气的分压分别如表1所示。由制作的试样的XRD图谱确认到形成了包含电阻率低的FeO相的被膜。
表1
Figure BDA0002357615020000071

Claims (3)

1.一种软磁性材料的制造方法，包括下述步骤：在包含水蒸气和惰性气体的气氛中加热软磁性合金基材，从而在所述软磁性合金基材上由来自软磁性合金基材的Fe形成α-Fe2O3单相膜，
所述气氛的氧分压在0～1.5kPa的范围内。
2.根据权利要求1所述的软磁性材料的制造方法，所述惰性气体为氮气。
3.根据权利要求1或2所述的软磁性材料的制造方法，所述气氛的露点为20～25℃。
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