JP2006336061A - Soft magnetic member - Google Patents
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- JP2006336061A JP2006336061A JP2005160937A JP2005160937A JP2006336061A JP 2006336061 A JP2006336061 A JP 2006336061A JP 2005160937 A JP2005160937 A JP 2005160937A JP 2005160937 A JP2005160937 A JP 2005160937A JP 2006336061 A JP2006336061 A JP 2006336061A
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本発明は、高磁束密度、高耐食性、高電気抵抗率を兼ね備えた軟磁性部材に関するものである。 The present invention relates to a soft magnetic member having high magnetic flux density, high corrosion resistance, and high electrical resistivity.
磁気回路を利用した製品には、軟磁性材料で成る部材（以下、軟磁性部材）が使用されている。この磁気回路製品に使用される軟磁性部材には、高い磁力を得るために高磁束密度であることが望まれる。
また、軟磁性部材に錆が発生すると、部材の形状変化によって磁気回路の作動に悪影響を及ぼすことから、長期間使用しても錆びることの無い耐食性に優れた軟磁性部材が望まれる。更に、磁気回路を高速駆動させた際に発生する渦電流を低く抑えて応答性の良い磁気回路とするためには、電気抵抗率の高い軟磁性部材が好ましい。
工業的には、純鉄、珪素鋼（質量％でＳｉ：３％、残部Ｆｅの合金）、パーマロイ（質量％でＮｉ：４０〜９０％、残部Ｆｅの合金）、パーメンダー（質量％でＣｏ：４９％、Ｖ：２％、残部Ｆｅの合金）、電磁ステンレス（質量％でＣｒ：１３〜１８％、残部Ｆｅ）等の材料が軟磁性材料として用いられている。
この内、最も優れた耐食性を示す部材は電磁ステンレスで成る軟磁性部材であるが、Ｃｒを１３〜１８％含む電磁ステンレス製の部材においては、その磁束密度が低いという欠点がある。また、磁束密度が最も高い軟磁性部材は、ＦｅとＣｏを主成分とするパーメンダー製の部材においては耐食性に乏しいという欠点がある。
In products using magnetic circuits, members made of soft magnetic materials (hereinafter referred to as soft magnetic members) are used. The soft magnetic member used in this magnetic circuit product is desired to have a high magnetic flux density in order to obtain a high magnetic force.
In addition, when rust occurs in the soft magnetic member, the change in the shape of the member adversely affects the operation of the magnetic circuit. Therefore, a soft magnetic member excellent in corrosion resistance that does not rust even after long-term use is desired. Furthermore, a soft magnetic member having a high electrical resistivity is preferable in order to suppress the eddy current generated when the magnetic circuit is driven at a high speed to obtain a magnetic circuit with good response.
Industrially, pure iron, silicon steel (mass% Si: 3%, balance Fe alloy), permalloy (mass% Ni: 40-90%, balance Fe alloy), permender (mass% Co: Materials such as 49%, V: 2%, balance Fe alloy), electromagnetic stainless steel (Cr: 13-18% in mass%, balance Fe), etc. are used as soft magnetic materials.
Among them, the member exhibiting the most excellent corrosion resistance is a soft magnetic member made of electromagnetic stainless steel, but a member made of electromagnetic stainless steel containing 13 to 18% of Cr has a drawback that its magnetic flux density is low. In addition, the soft magnetic member having the highest magnetic flux density has a drawback that it is poor in corrosion resistance in a member made of a permender mainly composed of Fe and Co.
これらの欠点を改善するため、軟磁性部材の素材である軟磁性材料の化学組成を改良することが提案されている。
例えば、特許文献１には、質量％でＣｏ：１０〜３５％、Ｓｉ，Ａｌ，Ｃｒ，Ｖ，Ｎｂ，Ｔｉの内の１種または２種以上を合計で１０％以下含み、残部が実質的にＦｅで成る軟磁性材料が開示されている。この特許文献１において選択元素として各合金元素（Ｓｉ，Ａｌ，Ｃｒ，Ｖ，Ｎｂ，Ｔｉ）を添加する目的は主に電気抵抗率を高めることにある。
また、特許文献２には、質量％でＣｒ：４〜１８％、Ｃｏ：４〜２６％を主体として、Ｓｉ：０．５〜８％、Ｍｏ：０．５〜８％、Ｍｎ：０．５〜８％、Ｔｉ：０．２〜２％、Ａｌ：０．２〜２％、Ｎｂ：０．２〜２％の内の１種以上を含み、残部がＦｅから成る軟磁性材料が開示されている。
In order to improve these defects, it has been proposed to improve the chemical composition of the soft magnetic material that is the material of the soft magnetic member.
For example, Patent Document 1 includes Co: 10 to 35% by mass and one or more of Si, Al, Cr, V, Nb, and Ti in total of 10% or less, and the balance is substantially the same. Discloses a soft magnetic material made of Fe. In this Patent Document 1, the purpose of adding each alloy element (Si, Al, Cr, V, Nb, Ti) as a selective element is mainly to increase electrical resistivity.
Patent Document 2 discloses that mass: Cr: 4 to 18%, Co: 4 to 26%, Si: 0.5 to 8%, Mo: 0.5 to 8%, Mn: 0.00. A soft magnetic material containing at least one of 5 to 8%, Ti: 0.2 to 2%, Al: 0.2 to 2%, Nb: 0.2 to 2%, and the balance being Fe is disclosed. Has been.
本発明者の検討によると、上述した特許文献１に開示される軟磁性材料は、電気抵抗率を高めることができる点では有利である。しかしながら、選択元素として記載された元素の添加の効果のみでは、Ｃｒを多量に（約４％以上）含む場合以外に耐食性を向上させることができなかった。また、優れた耐食性を得るためにＣｒ含有量を高めると磁束密度が低下するという問題が生じた。
また、特許文献２に開示される軟磁性材料は、高い電気抵抗率と優れた耐食性を有しているが、Ｃｒ含有量が４〜１８質量％と高いので、特許文献１と同様に磁束密度が低下するという問題があった。
本発明の目的は、高い磁束密度、高い耐食性、高い電気抵抗率を兼ね備えた軟磁性部材を提供することである。
According to the study of the present inventor, the soft magnetic material disclosed in Patent Document 1 described above is advantageous in that the electrical resistivity can be increased. However, the corrosion resistance cannot be improved only by the effect of addition of the element described as the selective element, except in the case of containing a large amount of Cr (about 4% or more). Further, when the Cr content is increased in order to obtain excellent corrosion resistance, there arises a problem that the magnetic flux density is lowered.
Moreover, although the soft magnetic material disclosed in Patent Document 2 has high electrical resistivity and excellent corrosion resistance, the Cr content is as high as 4 to 18% by mass. There was a problem that decreased.
An object of the present invention is to provide a soft magnetic member having high magnetic flux density, high corrosion resistance, and high electrical resistivity.
本発明者は、軟磁性部材として求められる高い磁束密度特性、高い電気抵抗率を得ながら、耐食性を高める方法を検討した結果、軟磁性部材の表面をＡｌとＯを主成分とする酸化皮膜で被覆することによって耐食性を大きく改善できること、そして、熱処理によってＡｌとＯを主成分とする酸化皮膜を生成させ、かつ高磁束密度と高電気抵抗率を得るための軟磁性部材の組成範囲を見出し、本発明に到達した。
即ち本発明は、少なくとも、質量％でＡｌ：０．１０〜３．０％、Ｃｏ：１０．０〜５５．０％とを含有し、残部が実質的にＦｅで成る軟磁性部材であって、該軟磁性部材の表面がＡｌとＯとを主成分とする酸化皮膜で覆われている軟磁性部材である。
好ましくは、上記の軟磁性部材は、更に質量％でＣｒ：０．１０〜３．０％を含む軟磁性部材である。
更に好ましくは、上記の軟磁性部材は、更に質量％でＶ：０．１０〜３．０％、Ｓｉ：０．１０〜３．０％の１種または２種を含む軟磁性部材である。
As a result of studying a method for improving the corrosion resistance while obtaining high magnetic flux density characteristics and high electrical resistivity required for a soft magnetic member, the present inventor has found that the surface of the soft magnetic member is an oxide film mainly composed of Al and O. Corrosion resistance can be greatly improved by coating, and an oxide film mainly composed of Al and O is generated by heat treatment, and a composition range of a soft magnetic member for obtaining a high magnetic flux density and a high electrical resistivity is found, The present invention has been reached.
That is, the present invention is a soft magnetic member containing at least Al: 0.10 to 3.0% and Co: 10.0 to 55.0% by mass, with the balance being substantially Fe. The soft magnetic member is covered with an oxide film containing Al and O as main components.
Preferably, the soft magnetic member is a soft magnetic member further containing Cr: 0.10 to 3.0% by mass.
More preferably, the soft magnetic member is a soft magnetic member further including one or two of V: 0.10 to 3.0% and Si: 0.10 to 3.0% by mass%.
本発明の軟磁性部材は、従来兼ね備えることができなかった、高い磁束密度、高い電気抵抗率、高い耐食性を兼備するため、磁気回路の基本性能向上に効果があり、磁気回路の応答性向上の効果も奏するものである。 The soft magnetic member of the present invention has high magnetic flux density, high electrical resistivity, and high corrosion resistance, which could not be conventionally combined. Therefore, the soft magnetic member is effective in improving the basic performance of the magnetic circuit and improving the response of the magnetic circuit. There is also an effect.
本発明の軟磁性部材は、高い磁束密度、高い電気抵抗率、高い耐食性を兼備する。これを実現するために、ＦｅとＣｏとを主成分として磁束密度を高め、これに、高い磁束密度を劣化させることなく、高い電気抵抗率と高い耐食性とを付与するために適量のＡｌを添加するものである。
以下、本発明における規定理由を述べる。なお、特に記載の無い限り各元素の含有量は質量％として記す。
Ａｌ：０．１０〜３．０％
Ａｌは、適量添加することで高い電気抵抗率を付与し、且つ熱処理によって軟磁性部材の表面に外方拡散し、ＡｌとＯを主成分とする酸化皮膜を生成させて高い耐食性を付与するために必要な本発明の必須元素である。但し、０．１０％未満では高い電気抵抗率の付与及び高い耐食性の付与の効果が小さく、逆に３．０％を超える範囲では軟磁性部材の磁束密度を低下させるので０．１０〜３．０％の範囲に規定した。より好ましくは、０．５０〜２．０％であると良い。
The soft magnetic member of the present invention has high magnetic flux density, high electrical resistivity, and high corrosion resistance. In order to achieve this, the magnetic flux density is increased with Fe and Co as the main components, and an appropriate amount of Al is added to impart high electrical resistivity and high corrosion resistance without deteriorating the high magnetic flux density. To do.
Hereinafter, the reason for the definition in the present invention will be described. Unless otherwise specified, the content of each element is expressed as mass%.
Al: 0.10 to 3.0%
Al is added in an appropriate amount to give a high electrical resistivity and to diffuse outwardly on the surface of the soft magnetic member by heat treatment to produce an oxide film composed mainly of Al and O to give high corrosion resistance. It is an essential element of the present invention necessary for the above. However, if it is less than 0.10%, the effect of imparting high electrical resistivity and imparting high corrosion resistance is small, and conversely if it exceeds 3.0%, the magnetic flux density of the soft magnetic member is lowered, so that it is 0.10-3. It was specified in the range of 0%. More preferably, it is 0.50 to 2.0%.
Ｃｏ：１０．０〜５５．０％
Ｃｏは、高磁束密度を得るために必要な本発明の必須元素である。また、Ｃｏは、熱処理時にＡｌの表面への外方拡散を助長する効果も併せ持っている。但し、１０．０％未満では磁束密度を高める効果が小さく、逆に５５．０％を超える範囲では磁束密度を低下させるので、含有量を１０．０〜５５．０％に規定した。Ｃｏ量のより望ましい範囲は２０．０〜５０．０％であり、更に望ましくは、２５．０〜５０．０％であると良い。
残部：実質的にＦｅ
本発明の軟磁性部材では、上記の必須添加する元素以外の残部は実質的にＦｅとして、Ｆｅ及びＣｏが主成分の合金系として高い磁束密度を実現する。なお、本発明では残部は実質的にＦｅとするが、Ｃ，Ｓｉ，Ｍｎ，Ｐ，Ｓ，Ｎ，Ｏ等の不可避不純物は当然ながら含まれる。
この不純物元素のうち、特に制限が必要なものはＡｌと非金属介在物を形成するＯとＮであり、過度に含有すれば耐酸化性向上に寄与するＡｌとＯとを主成分とする酸化皮膜形成に悪影響を及ぼす。そのため、ＯとＮはそれぞれ０．０３％以下（０を含む）とし、好ましくは０．０１％以下とすれば良い。
また、ＯとＮ以外の不可避不純物は、軟磁性部材の磁束密度と耐食性に悪影響を及ぼさない範囲として、それぞれＣ≦０．１０％（０を含む）、Ｍｎ≦１．０％（０を含む）、Ｐ≦０．１０％（０を含む）、Ｓ≦０．１０％（０を含む）の範囲で含有しても良い。
Co: 10.0-55.0%
Co is an essential element of the present invention necessary for obtaining a high magnetic flux density. Co also has the effect of promoting outward diffusion of Al to the surface during heat treatment. However, if the content is less than 10.0%, the effect of increasing the magnetic flux density is small, and conversely, if the content exceeds 55.0%, the magnetic flux density is lowered. Therefore, the content is defined as 10.0 to 55.0%. A more desirable range of the amount of Co is 20.0 to 50.0%, and further desirably 25.0 to 50.0%.
The rest: substantially Fe
In the soft magnetic member of the present invention, the remainder other than the above essential elements is substantially Fe, and a high magnetic flux density is realized as an alloy system mainly composed of Fe and Co. In the present invention, the balance is substantially Fe, but naturally unavoidable impurities such as C, Si, Mn, P, S, N, and O are included.
Of these impurity elements, the elements that need to be particularly restricted are O and N that form non-metallic inclusions with Al, and oxidation containing Al and O as main components that contribute to improving oxidation resistance if excessively contained. It adversely affects film formation. Therefore, O and N are each 0.03% or less (including 0), preferably 0.01% or less.
In addition, inevitable impurities other than O and N are C ≦ 0.10% (including 0) and Mn ≦ 1.0% (including 0) as ranges that do not adversely affect the magnetic flux density and corrosion resistance of the soft magnetic member. ), P ≦ 0.10% (including 0), S ≦ 0.10% (including 0).
本発明では、上述した化学組成を有する軟磁性材料の素材表面にＡｌとＯを主成分とする酸化皮膜を形成してＡｌとＯとを主成分とする酸化皮膜により優れた耐食性を確保する。
ＡｌとＯを主成分とする酸化皮膜は緻密な酸化物で構成され、かつ基地との密着性も良好であることから、耐食性保護皮膜として有効な役割を果たす。このような酸化皮膜は、本発明範囲の組成をもつ軟磁性部材を熱処理することによって生成することができる。
この熱処理時の温度と保持時間は、それぞれ温度：７００〜９５０℃、保持時間：０．５〜５ｈであることが望ましい。その理由は、温度が７００℃未満や保持時間が０．５ｈ未満の場合には、Ａｌを表面に外方拡散させてＡｌとＯを主成分とする皮膜を生成させる効果が小さく、逆に温度が９５０℃を超える場合や保持時間が５ｈを超える場合には、ＡｌとＯを主成分とする酸化皮膜は生成するものの、高温・長時間の熱処理で形成した酸化皮膜によってより一層の耐酸化性向上の効果は期待できず、熱処理に必要とされるエネルギー消費量も増して経済的ではない。そのため、温度：７００〜９５０℃、保持時間：０．５〜５ｈであることが望ましい。
In the present invention, an oxide film mainly composed of Al and O is formed on the surface of the soft magnetic material having the above-described chemical composition, and excellent corrosion resistance is ensured by the oxide film mainly composed of Al and O.
Since the oxide film containing Al and O as main components is composed of a dense oxide and has good adhesion to the matrix, it plays an effective role as a corrosion-resistant protective film. Such an oxide film can be produced by heat-treating a soft magnetic member having a composition within the range of the present invention.
The temperature and holding time during the heat treatment are desirably temperature: 700 to 950 ° C. and holding time: 0.5 to 5 h, respectively. The reason for this is that when the temperature is less than 700 ° C. or the holding time is less than 0.5 h, the effect of causing Al to diffuse outwardly to form a film mainly composed of Al and O is small. When the temperature exceeds 950 ° C. or the holding time exceeds 5 hours, an oxide film composed mainly of Al and O is produced, but the oxidation film formed by heat treatment for a long time at a high temperature further enhances the oxidation resistance. The improvement effect cannot be expected, and the energy consumption required for the heat treatment increases, which is not economical. Therefore, it is desirable that the temperature is 700 to 950 ° C. and the holding time is 0.5 to 5 hours.
また、熱処理を行う雰囲気は、例えば酸素と窒素が合計で０．１ｖｏｌ％以下、残部が実質的に水素（純度３Ｎ以上）の還元性雰囲気中で、露点−２０℃以下で処理すると良い。
その理由は、このような酸素分圧の低い雰囲気で熱処理を行うと、最も酸化し易いＡｌのみが酸化されるからであり、例えば大気中や、純度３Ｎ以下の水素雰囲気等、酸素分圧の高い雰囲気で熱処理を行うと、Ａｌの他にＦｅも酸化する結果、ＡｌとＯを主成分とする緻密な酸化皮膜が生成せず、ＦｅとＯを主成分とする疎な形態の酸化物が生成するために耐食性向上の効果が得られ難いからである。また、酸素分圧の高い雰囲気下での熱処理は、部材の軟磁性にも悪影響を及ぼす。それ故、上述の雰囲気が望ましい。
また、本発明で言うＡｌとＯを主成分とする酸化皮膜とは、軟磁性部材の表面濃度を光電子分光装置（ＥＳＣＡ）で測定した際、原子％でＡｌ量が３０％以上であり且つＯ量が５０％以上である酸化皮膜を指す。なお、形成するＡｌとＯとを主成分とする酸化皮膜の好ましい厚みについては、ＳｉＯ２標準試料を用いた光電子分光装置（ＥＳＣＡ）で測定した場合、その下限は５ｎｍ以上（好ましくは２０ｎｍ以上）、上限は５００ｎｍ以下（好ましくは３００ｎｍ以下）であればよい。
また、ＡｌとＯとを主成分とする酸化皮膜の色は、分光測色計により測定される反射率Ｙが３０〜４０％、ｘ色度が０．３以下（好ましくは０．２〜０．３）、ｙ色度が０．３５以下（好ましくは０．２〜０．３）の範囲内にある薄青〜青色部分となるのが望ましい。
The atmosphere for the heat treatment is preferably a dew point of −20 ° C. or less in a reducing atmosphere in which oxygen and nitrogen are combined in a total amount of 0.1 vol% or less and the balance is substantially hydrogen (purity 3N or more).
The reason is that when heat treatment is performed in an atmosphere having such a low oxygen partial pressure, only the most easily oxidized Al is oxidized. For example, in the air or a hydrogen atmosphere having a purity of 3N or less, the oxygen partial pressure is low. When heat treatment is performed in a high atmosphere, Fe is oxidized in addition to Al. As a result, a dense oxide film mainly composed of Al and O is not formed, and a sparse form oxide mainly composed of Fe and O is formed. This is because it is difficult to obtain the effect of improving the corrosion resistance. In addition, heat treatment under an atmosphere having a high oxygen partial pressure adversely affects the soft magnetism of the member. Therefore, the above atmosphere is desirable.
The oxide film mainly composed of Al and O in the present invention means that when the surface concentration of a soft magnetic member is measured by a photoelectron spectrometer (ESCA), the Al content is 30% or more in atomic% and O It refers to an oxide film whose amount is 50% or more. Note that the preferred thickness of the oxide film mainly composed of Al and O to form, when measured by SiO 2 photoelectron spectrometer using a standard sample (ESCA), the lower limit of more than 5 nm (preferably at least 20 nm) The upper limit may be 500 nm or less (preferably 300 nm or less).
The color of the oxide film mainly composed of Al and O has a reflectance Y measured by a spectrocolorimeter of 30 to 40% and an x chromaticity of 0.3 or less (preferably 0.2 to 0). .3), it is desirable that the y chromaticity is a light blue to blue portion in the range of 0.35 or less (preferably 0.2 to 0.3).
次に、より望ましい組成範囲を規定した理由を述べる。
Ｃｒ：０．１０〜３．０％
Ｃｒは、軟磁性部材の耐食性を向上させ、かつ電気抵抗率を高める元素である。但し、含有量が０．１０％未満の場合には、いずれの効果も小さく、逆に３．０％を超える場合には、磁束密度を顕著に低下させるので上述の範囲に規定した。Ｃｒ量のより望ましい範囲は、０．５０〜２．０％である。
Ｖ：０．１０〜３．０％
Ｖは、軟磁性部材の電気抵抗率を高め、更に冷間加工性を向上させる効果を持っている。但し、０．１０％未満では、いずれの効果も小さく、逆に３．０％を超える範囲では、磁束密度を顕著に低下させるので、上述の範囲に規定した。より望ましい範囲は、０．５０〜２．５０％である。
Ｓｉ：０．０５〜３．０％
Ｓｉも、軟磁性部材の電気抵抗率を高めるのに有効な元素である。但し、その含有量が０．０５％未満では効果が小さく、逆に３．０％を超える範囲では磁束密度を顕著に低下させるので上述の範囲に規定した。Ｓｉ量のより望ましい範囲は、０．１０〜２．５０％であり、更に望ましくは０．５０〜２．０％である。
Next, the reason for defining a more desirable composition range will be described.
Cr: 0.10 to 3.0%
Cr is an element that improves the corrosion resistance of the soft magnetic member and increases the electrical resistivity. However, when the content is less than 0.10%, all the effects are small. On the contrary, when the content exceeds 3.0%, the magnetic flux density is remarkably lowered. A more desirable range of the Cr content is 0.50 to 2.0%.
V: 0.10 to 3.0%
V has the effect of increasing the electrical resistivity of the soft magnetic member and further improving the cold workability. However, if the content is less than 0.10%, all the effects are small. Conversely, if the content exceeds 3.0%, the magnetic flux density is remarkably lowered. A more desirable range is 0.50 to 2.50%.
Si: 0.05-3.0%
Si is also an effective element for increasing the electrical resistivity of the soft magnetic member. However, if the content is less than 0.05%, the effect is small. Conversely, if the content exceeds 3.0%, the magnetic flux density is remarkably lowered, so the above range is specified. A more preferable range of the amount of Si is 0.10 to 2.50%, and more preferably 0.50 to 2.0%.
以下の実施例で本発明を更に詳しく説明する。
真空溶解炉を用いて、１０ｋｇの材料を１２種類溶製した。各溶製材の化学組成を表１に示す。
なお、Ｎｏ．１〜５は、Ａｌ量を約１％に固定し、Ｃｏ量を１２．０２〜４９．０１％の範囲で変動させた材料である。これら５種類の材料では、ＣｒとＶは無添加とし、Ｓｉは０．１０％以下とした。
また、Ｎｏ．６は、Ｎｏ．３のＡｌ量を高めた材料である。Ｎｏ．７〜９は、Ｎｏ．３の組成を基本として、それぞれ１．９６％Ｃｒ（Ｎｏ．７）、２．１１％Ｖ＋１．４８％Ｓｉ（Ｎｏ．８）、２．０４％Ｃｒ＋１．４９％Ｓｉ（Ｎｏ．９）の各元素を加えた材料である。
Ｎｏ．１０は、Ａｌ量を０．５５％、Ｃｏ量を２５．０２％、Ｓｉ量を０．５１％とし、Ｃｒ量を８．２１％まで高めた材料であり、化学組成は本発明の範囲外である。
更にＮｏ．１１は、Ｆｅ−１３％Ｃｒを主成分とする電磁ステンレスに相当し、Ｎｏ．１２は、Ｆｅ−４９％Ｃｏ−２％Ｖを主成分とするパーメンダーに相当し、化学組成は本発明の範囲外である。
The following examples further illustrate the present invention.
Using a vacuum melting furnace, 12 kinds of 10 kg materials were melted. Table 1 shows the chemical composition of each melted material.
In addition, No. Nos. 1 to 5 are materials in which the Al amount is fixed to about 1% and the Co amount is varied in the range of 12.02 to 49.01%. In these five types of materials, Cr and V were not added, and Si was 0.10% or less.
No. 6 is No.6. 3 is a material with an increased amount of Al. No. 7 to 9 are No. 3, each of 1.96% Cr (No. 7), 2.11% V + 1.48% Si (No. 8), 2.04% Cr + 1.49% Si (No. 9), respectively. It is a material with added elements.
No. 10 is a material in which the Al amount is 0.55%, the Co amount is 25.02%, the Si amount is 0.51%, and the Cr amount is increased to 8.21%, and the chemical composition is outside the scope of the present invention. It is.
Furthermore, no. No. 11 corresponds to an electromagnetic stainless steel mainly composed of Fe-13% Cr. No. 12 corresponds to a permender whose main component is Fe-49% Co-2% V, and the chemical composition is outside the scope of the present invention.
これら１２種類の溶製材を１１００℃に加熱して熱間鍛造を行い、直径２５ｍｍの丸棒材を得た。これらの丸棒材から、以下に示す２種類の工程（Ａ，Ｂ）により、諸特性評価用の各軟磁性部材を作製した。
＜工程Ａ＞
熱間鍛造後の丸棒材から、磁束密度と電気抵抗率測定用の１ｍｍ×８ｍｍ×８０ｍｍの板状部材と塩水噴霧試験と表面濃度プロファイル測定用の１ｍｍ×φ２０ｍｍの円板状部材を放電加工機により切り出し、各部材の表面をエメリー紙で＃５００まで一方向研磨した。これらの部材を純度４Ｎ、露点−４０℃の水素雰囲気（雰囲気中に含まれる不純物は、酸素０．０１ｐｐｍ，窒素２．０４ｐｐｍ）において、温度８５０℃、保持３時間の条件で熱処理した後に炉冷して軟磁性部材とした。
These 12 kinds of melted materials were heated to 1100 ° C. and hot forged to obtain round bars with a diameter of 25 mm. From these round bars, soft magnetic members for evaluating various properties were produced by the following two steps (A, B).
<Process A>
From a round bar after hot forging, a 1 mm x 8 mm x 80 mm plate member for measuring magnetic flux density and electrical resistivity and a 1 mm x φ20 mm disk member for salt spray test and surface concentration profile measurement are electrodischarge machined. The surface of each member was unidirectionally polished up to # 500 with emery paper. These members were heat-treated in a hydrogen atmosphere with a purity of 4N and a dew point of −40 ° C. (impurities contained in the atmosphere were oxygen 0.01 ppm and nitrogen 2.04 ppm) at a temperature of 850 ° C. and a holding time of 3 hours. Thus, a soft magnetic member was obtained.
＜工程Ｂ＞
熱間鍛造後の丸棒材の一部を切断して８５０℃に保持した大気炉中で３時間保持後に炉冷し、この熱処理後の丸棒材から磁束密度と電気抵抗率測定用の１ｍｍ×８ｍｍ×８０ｍｍの板状部材と塩水噴霧試験と表面濃度分析用の１ｍｍ×φ２０ｍｍの円板状部材を放電加工機により切り出し、各部材の表面をエメリー紙で＃５００まで一方向研磨して軟磁性部材とした。
工程Ａと工程Ｂでは、熱処理雰囲気を除いて熱間鍛造後の加工方法、熱処理温度、保持時間、冷却方法は同じであるが、部材の加工（切り出し）と熱処理の順序が異なっている。以下、表１に示したＮｏ．１〜１２の数字と工程Ａ，Ｂを組み合わせ、１Ａ，１Ｂ，〜１２Ａ，１２Ｂの２４種類の記号を用いて各軟磁性部材を表記する。
<Process B>
A portion of the round bar material after hot forging was cut and held in an atmospheric furnace maintained at 850 ° C. for 3 hours and then cooled in the furnace. From the round bar material after the heat treatment, 1 mm for measuring magnetic flux density and electrical resistivity. A plate-shaped member of × 8 mm × 80 mm and a disk-shaped member of 1 mm × φ20 mm for salt spray test and surface concentration analysis are cut out with an electric discharge machine, and the surface of each member is unidirectionally polished to # 500 with emery paper and softened. A magnetic member was used.
In step A and step B, the processing method after hot forging, the heat treatment temperature, the holding time, and the cooling method are the same except for the heat treatment atmosphere, but the order of member processing (cutting) and heat treatment is different. Hereinafter, No. 1 shown in Table 1. Each of the soft magnetic members is described using a combination of the numbers 1 to 12 and the processes A and B, using 24 kinds of symbols 1A, 1B, to 12A, and 12B.
工程Ａで作製した軟磁性部材の内、１Ａ〜１０Ａの１０種類の軟磁性部材は、表面が薄青く着色していた。この内、軟磁性部材８Ａの表面の反射率Ｙ、ｘ色度、ｙ色度を分光測色計（ミノルタ製ＣＭ−２００２）により測定したところ、Ｙ＝３４．７９％、ｘ＝０．２６５、ｙ＝０．２９１５であった。また、着色した軟磁性部材の表面を電界放射型走査型電子顕微鏡（ＦＥ−ＳＥＭ）により加速電圧５ｋＶの条件で観察した例として、軟磁性部材８Ａの観察結果を図１に示す。図１から、軟磁性部材８Ａの表面は、粒径１００ｎｍ程度の緻密な微粒子で被覆されていることが分かる。
この軟磁性部材８Ａの表面からの濃度プロファイルを光電子分光分析装置（ＥＳＣＡ）により１２００秒間スパッタして測定した結果を図２に示す。なお、測定時のスパッタ速度は、ＳｉＯ２標準試料が毎分１ｎｍの速さでスパッタされる速度に調整されている。
図２より、軟磁性部材８Ａの表面濃度は、原子％でＡｌ量が３０％以上、Ｏ量が５０％以上となっており、ＡｌとＯを主成分とする酸化皮膜で被覆されており、ＡｌとＯを主成分とする酸化皮膜の厚みは２０ｎｍ以上であることが分かる。実際に、軟磁性部材８Ａの酸化皮膜の断面を電界放射型走査電子顕微鏡により、加速電圧１５ｋＶで観察したところ、図５に示すように、約１００ｎｍの酸化皮膜が生成していた。
この内、３０秒間スパッタ後、および１２００秒間スパッタ後の状態において、酸化皮膜の結合エネルギーのピーク位置を図３に示す。図３より、ＡｌとＯの結合エネルギーのピーク位置がＡｌ２Ｏ３（アルミナ）と一致することから、軟磁性部材の表面を被覆する上記の酸化皮膜は、Ａｌ２Ｏ３であることが分かる。
他の着色した軟磁性部材１Ａ〜７Ａと９Ａ〜１０Ａにおいても、同様にＡｌ２Ｏ３皮膜が生成していた。それ故、表面が薄青く着色した１０種類の軟磁性部材の内、化学組成が本発明の範囲に含まれるＮｏ．１Ａ〜９Ａは本発明例である。
Among the soft magnetic members produced in step A, 10 types of soft magnetic members 1A to 10A were colored light blue. Among these, the reflectance Y, x chromaticity, and y chromaticity of the surface of the soft magnetic member 8A were measured with a spectrocolorimeter (CM-2002 manufactured by Minolta). Y = 34.79%, x = 0.265 Y = 0.2915. FIG. 1 shows an observation result of the soft magnetic member 8A as an example of observing the surface of the colored soft magnetic member with a field emission scanning electron microscope (FE-SEM) under an acceleration voltage of 5 kV. As can be seen from FIG. 1, the surface of the soft magnetic member 8A is covered with dense fine particles having a particle diameter of about 100 nm.
FIG. 2 shows the result of measuring the concentration profile from the surface of the soft magnetic member 8A by sputtering for 1200 seconds with a photoelectron spectrometer (ESCA). The sputtering rate at the time of measurement is adjusted to a rate at which the SiO 2 standard sample is sputtered at a rate of 1 nm per minute.
From FIG. 2, the surface concentration of the soft magnetic member 8A is atomic%, the amount of Al is 30% or more, the amount of O is 50% or more, and is covered with an oxide film mainly composed of Al and O. It can be seen that the thickness of the oxide film composed mainly of Al and O is 20 nm or more. Actually, when the cross section of the oxide film of the soft magnetic member 8A was observed at an acceleration voltage of 15 kV with a field emission scanning electron microscope, an oxide film of about 100 nm was formed as shown in FIG.
Among these, the peak position of the binding energy of the oxide film is shown in FIG. 3 after being sputtered for 30 seconds and after being sputtered for 1200 seconds. From FIG. 3, since the peak position of the binding energy of Al and O coincides with Al 2 O 3 (alumina), it can be seen that the above oxide film covering the surface of the soft magnetic member is Al 2 O 3. .
In the other colored soft magnetic members 1A to 7A and 9A to 10A, Al 2 O 3 films were similarly formed. Therefore, among the 10 types of soft magnetic members colored light blue, the chemical composition is included in the scope of the present invention. 1A to 9A are examples of the present invention.
一方、１１Ａ，１２Ａと工程Ｂにより作製した軟磁性部材１Ｂ〜１２Ｂは、着色していなかった。これら未着色の軟磁性部材における表面濃度の測定例として、軟磁性部材８Ｂの表面の濃度プロファイルを図４に示す。スパッタ時間の進行とともに酸素量は低減し、ＦｅとＣｏの濃度が上昇している。図４から、軟磁性部材８Ｂの表面にＡｌとＯを主成分とする酸化皮膜は生成しておらず、本発明の比較例である。
他の未着色の軟磁性部材においても、表面にＡｌとＯを主成分とする酸化皮膜は生成していなかった。それ故、未着色の軟磁性部材（１１Ａ，１２Ａ，１Ｂ〜１２Ｂ）、および表面にＡｌとＯを主成分とする酸化皮膜が生成しているものの化学組成が本発明範囲から外れる軟磁性部材１０Ａは、本発明の比較例である。
On the other hand, the soft magnetic members 1B to 12B produced by 11A and 12A and the process B were not colored. As an example of measuring the surface concentration of these uncolored soft magnetic members, the concentration profile of the surface of the soft magnetic member 8B is shown in FIG. As the sputtering time progresses, the amount of oxygen decreases and the concentration of Fe and Co increases. From FIG. 4, the oxide film which has Al and O as a main component is not produced | generated on the surface of the soft-magnetic member 8B, and is a comparative example of this invention.
Also in other uncolored soft magnetic members, an oxide film mainly composed of Al and O was not formed on the surface. Therefore, the uncolored soft magnetic member (11A, 12A, 1B to 12B) and the soft magnetic member 10A whose chemical composition deviates from the scope of the present invention although the surface is formed with an oxide film mainly composed of Al and O. These are comparative examples of the present invention.
作製した２４種類の軟磁性部材の表面に温度３５℃の５％ＮａＣｌ溶液を噴霧して錆の発生状況を確認した。また、直流磁束計を用いて、各軟磁性部材に１０，０００Ａ／ｍの磁場を印加し、磁束密度Ｂ１００００（Ｔ）を測定した。更に、４端子法の電気抵抗測定装置を用いて、各軟磁性部材に５００ｍＡの定電流を流し、両端の電位差を測定することにより電気抵抗率ρ（μΩｍ）を測定した。
各軟磁性部材の塩水噴霧試験結果（２時間後と２４時間後）、磁束密度Ｂ１００００（Ｔ）、電気抵抗率ρ（μΩｍ）を一覧にして表２に示す。なお、塩水噴霧試験結果については、全く錆びていないものを○、一部が錆びているものを△、ほぼ全面が錆びているものを×として示す。
Rust generation was confirmed by spraying a 5% NaCl solution at a temperature of 35 ° C. on the surface of the 24 types of soft magnetic members produced. Further, a magnetic field of 10,000 A / m was applied to each soft magnetic member using a DC magnetometer, and the magnetic flux density B 10000 (T) was measured. Furthermore, using a four-terminal electrical resistance measuring device, a constant current of 500 mA was passed through each soft magnetic member, and the electrical potential ρ (μΩm) was measured by measuring the potential difference between both ends.
Table 2 shows a list of salt spray test results (after 2 hours and 24 hours), magnetic flux density B 10000 (T), and electrical resistivity ρ (μΩm) of each soft magnetic member. In addition, about the salt spray test result, what does not rust at all is shown as (circle), what is partly rusted as (triangle | delta), and what has almost rusted as x.
表２から、本発明の１Ａ〜９Ａでは、２時間の塩水噴霧後には全く錆びていない。また、２４時間の塩水噴霧後にも１Ａ〜６Ａと８Ａでは試験片の一部が錆びる程度に留まっており、より好ましい組成範囲とした７Ａと９Ａでは、全く錆びていない。これに対し、比較例の１２Ａ，１Ｂ〜９Ｂ，１２Ｂでは、２時間の塩水噴霧によって試験片のほぼ全面が錆びている。また、１０Ｂの耐食性も本発明の１Ａ〜９Ａと比較して劣っている。
一方、比較例の１０Ａ，１１Ａ，１１Ｂの耐食性は、本発明の１Ａ〜９Ａよりも優れているが、これらの軟磁性部材の磁束密度Ｂ１００００は、それぞれ１．５５Ｔ（１０Ａ）、１．４８Ｔ（１１Ａと１１Ｂ）であり、本発明の軟磁性部材（１Ａ〜９Ａ）の１．８１〜２．３７Ｔと比較して低い結果となった。
From Table 2, 1A to 9A of the present invention is not rusted after 2 hours of salt water spraying. Further, even after spraying with salt water for 24 hours, in 1A to 6A and 8A, only a part of the test piece remains rusted, and in 7A and 9A having a more preferable composition range, there is no rust. On the other hand, in the comparative examples 12A, 1B to 9B, 12B, almost the entire surface of the test piece is rusted by salt water spray for 2 hours. Moreover, the corrosion resistance of 10B is also inferior compared with 1A-9A of this invention.
On the other hand, the corrosion resistance of Comparative Examples 10A, 11A, and 11B is superior to 1A to 9A of the present invention, but the magnetic flux density B 10000 of these soft magnetic members is 1.55T (10A) and 1.48T, respectively. (11A and 11B), which was lower than 1.81 to 2.37T of the soft magnetic members (1A to 9A) of the present invention.
以上の結果から、化学組成を本発明の範囲内とし、かつ表面をＡｌとＯを主成分とする酸化皮膜で被覆した軟磁性部材とすることによって、高磁束密度と高耐食性を兼ね備えた軟磁性部材が得られていることが分かる。 From the above results, a soft magnetic member having a high magnetic flux density and a high corrosion resistance can be obtained by making a soft magnetic member having a chemical composition within the scope of the present invention and having a surface coated with an oxide film mainly composed of Al and O. It turns out that the member is obtained.
本発明の軟磁性部材は、高磁束密度と耐食性に優れており、更に高電気抵抗率化もできるので、これらの諸特性が必要とされる磁気回路の軟磁性部材として適用することができる。 The soft magnetic member of the present invention is excellent in high magnetic flux density and corrosion resistance, and can be further increased in electrical resistivity, so that it can be applied as a soft magnetic member for a magnetic circuit that requires these characteristics.
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| JP2020202314A (en) * | 2019-06-11 | 2020-12-17 | 鈴木 茂 | Method for manufacturing plate material for laminate iron core, plate material for laminate iron core, and laminate iron core |
| JP7271064B2 (en) | 2019-06-11 | 2023-05-11 | 茂 鈴木 | METHOD FOR MANUFACTURING PLATE MATERIAL FOR LAMINATED CORE, PLATE MATERIAL FOR LAMINATED CORE, AND LAMINATED CORE |
| JP7047959B1 (en) | 2021-03-31 | 2022-04-05 | Tdk株式会社 | Soft magnetic alloys and magnetic parts. |
| JP2022157041A (en) * | 2021-03-31 | 2022-10-14 | Tdk株式会社 | Soft magnetic alloy and magnetic component |
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