JP4319206B2 - Soft magnetic Fe-based metallic glass alloy - Google Patents
Soft magnetic Fe-based metallic glass alloy Download PDFInfo
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- JP4319206B2 JP4319206B2 JP2006198792A JP2006198792A JP4319206B2 JP 4319206 B2 JP4319206 B2 JP 4319206B2 JP 2006198792 A JP2006198792 A JP 2006198792A JP 2006198792 A JP2006198792 A JP 2006198792A JP 4319206 B2 JP4319206 B2 JP 4319206B2
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Description
本発明は、高飽和磁化で、軟磁気特性に優れた軟磁性Ｆｅ基金属ガラス合金に関する。 The present invention relates to a soft magnetic Fe-based metallic glass alloy having high saturation magnetization and excellent soft magnetic properties.
多元素合金のある種のものは、組成物を溶融状態から急冷するとき、結晶化せず、一定
の温度幅を有する過冷却液体状態を経過してガラス状固体に転移する性質を有していて、
この種の非晶質合金は「金属ガラス合金」（glassy alloy）と呼ばれている。
Certain types of multi-element alloys have the property that when the composition is rapidly cooled from the molten state, it does not crystallize and transitions to a glassy solid after passing through a supercooled liquid state having a certain temperature range. And
This type of amorphous alloy is called a “glassy alloy”.
「金属ガラス合金」は加熱によって明瞭なガラス転移が観察され、結晶化温度までの過
冷却液体領域の温度範囲が数十Ｋにも達する。この物性を備えることにより初めて、冷却
速度の遅い銅金型等に鋳込む方法によってバルク状のアモルファス合金を作ることができ
るようになった。このようなアモルファス合金が、特に、「金属ガラス」と呼ばれている
のは、金属でありながら、酸化物ガラスのように安定な非晶質で、高温で容易に塑性変形
（粘性流動）できるためである。
In the “metal glass alloy”, a clear glass transition is observed by heating, and the temperature range of the supercooled liquid region up to the crystallization temperature reaches several tens of K. For the first time with this physical property, a bulk amorphous alloy can be made by a method of casting into a copper mold having a slow cooling rate. Such an amorphous alloy is particularly called a “metal glass”, although it is a metal, it is a stable amorphous material like oxide glass and can be easily plastically deformed (viscous flow) at high temperatures. Because.
「金属ガラス合金」は、ガラス形成能が高い、すなわち、ガラス相からなる、より寸法
の大きな、いわゆるバルクの金属鋳造体を銅金型鋳造法等により溶湯から過冷却液体状態
において冷却凝固して製造できる特性を有するものであり、また、過冷却液体状態に加熱
して塑性加工できる特性を有するものであり、これらの特性を有しない従来の薄帯やファ
イバーなどの「アモルファス合金」とは本質的に異なる材料であり、その有用性も非常に
大きい。
“Metal glass alloy” has a high glass forming ability, that is, a so-called bulk metal casting made of a glass phase and having a larger size is cooled and solidified in a supercooled liquid state from a molten metal by a copper mold casting method or the like. It has the characteristics that can be manufactured, and has the characteristics that can be plastically processed by heating to a supercooled liquid state, and the essence of the conventional “amorphous alloys” such as ribbons and fibers that do not have these characteristics The material is very different and its usefulness is very great.
本発明者らが１９９５年にＦｅ−（Ａｌ，Ｇａ）系の軟磁性Ｆｅ基金属ガラス合金を報
告（非特許文献１、特許文献１〜３）して以来、機能材料（非特許文献２〜６）及び構造
材料（非特許文献７〜１０）として多数のＦｅ基金属ガラス合金が開発された。
Since the present inventors reported a Fe— (Al, Ga) -based soft magnetic Fe-based metallic glass alloy in 1995 (Non-patent
軟磁性Ｆｅ基金属ガラス合金は２つのグループに区別できる。一つは、Ｆｅ−Ｐ−Ｃ系
金属ガラス合金グループであり、他方は、新しく開発されたＦｅ−Ｂ−Ｓｉ系金属ガラス
合金グループである。Ｆｅ−Ｂ−Ｓｉ系金属ガラス合金は、直径又は厚さ２〜５ｍｍの金
属ガラス棒材に鋳造できる高いガラス形成能を有しているが、Ｂ、Ｓｉの含有量を多くす
る必要があり、Ｆｅ含有量が少ない（６５ａｔ％未満）ので、飽和磁化（Ｉｓ）は０．８
〜１．１Ｔとそれほど大きくなく、センサ用途としては有用であるが、電力変圧器やモー
ターへは適用できない。
Soft magnetic Fe-based metallic glass alloys can be distinguished into two groups. One is a Fe—P—C-based metallic glass alloy group, and the other is a newly developed Fe—B—Si based metallic glass alloy group. Fe-B-Si-based metallic glass alloy has a high glass-forming ability that can be cast into a metallic glass rod having a diameter or thickness of 2 to 5 mm, but it is necessary to increase the content of B and Si. Since the Fe content is low (less than 65 at%), the saturation magnetization (Is) is 0.8.
Although it is not so large as -1.1T and is useful as a sensor application, it cannot be applied to a power transformer or a motor.
低いヒシテリシス損失及び高いＩｓが電磁的エネルギー転換機器の低鉄損コアに必要な
基本的な特性であり、Ｆｅ基軟磁性金属ガラス合金は通常の多結晶Ｆｅ（Ｓｉ）合金によ
り製造されたものより低鉄損のコアを提供すべくその潜在可能性について研究されている
。それゆえ、Ｆｅ−Ｂ−Ｓｉ系金属ガラス合金と比べて、先行して開発されたＦｅ−Ｐ−
Ｃ系金属ガラス合金は、１．３〜１．４Ｔ（非特許文献３，１１）の高いＩｓを示すので
、磁気コア材としての応用は、より潜在可能性がある。
Low hysteresis loss and high Is are basic characteristics required for low iron loss core of electromagnetic energy conversion equipment, Fe-based soft magnetic metallic glass alloys are more than those produced by ordinary polycrystalline Fe (Si) alloys Its potential is being researched to provide a low iron loss core. Therefore, compared to Fe-B-Si-based metallic glass alloys, Fe-P- developed in advance.
Since the C-based metallic glass alloy exhibits a high Is of 1.3 to 1.4 T (Non-patent
しかしながら、Ｆｅ−Ｐ−Ｃ基金属ガラス合金の多くは、非常に高価なＧａを含有して
おり、そのコストは合金のコストの９０％を占める。Ｇａは、また、保磁力（Ｈｃ）の好
ましくない増加をもたらす（非特許文献１２）。さらにガラス形成能はそれほど大きくな
く、銅鋳型鋳造法により製造されたＦｅ−Ｐ−Ｃ基金属ガラス合金の最大直径又は厚さは
２．５ｍｍである（非特許文献３，１１）。
However, many of the Fe-PC-based metallic glass alloys contain very expensive Ga, and the cost accounts for 90% of the alloy cost. Ga also causes an undesirable increase in coercivity (Hc) (Non-patent Document 12). Furthermore, the glass forming ability is not so great, and the maximum diameter or thickness of the Fe—PC—C based metallic glass alloy produced by the copper mold casting method is 2.5 mm (Non-patent
一つのＦｅＣｒＭｏＧａＰＣＢＳｉ金属ガラス合金はより大きなガラス形成能を示し、
フラックス溶融及び水急冷で直径又は厚さ４ｍｍまでの金属ガラス合金を製造できるけれ
ども、この方法は、複雑であり、Ｉｓは低い（１Ｔ未満）。本発明者等は，これまで軟磁
性Ｆｅ基金属ガラス合金の開発を精力的に行なってきた（特許文献４〜１０）。特に、特
許文献９に示されるＦｅ−Ｂ−Ｓｉ系金属ガラス合金は１．４Ｔ以上の飽和磁化を有し、
保磁力が３．５〜３．０Ａ／ｍであり、Ｎｂを１ａｔ％を含有する合金は、図８に示す磁
化曲線に示す優れた軟磁気特性を有している。また、本発明者らは、組成がＦｅ７６−ｙ
｛（ＳｉａＢｂ）ｍ（ＰｃＣｄ）ｎ｝ｘＭｙ［Ｍ；Ｎｂ，Ｍｏ、１９≦ｘ≦３０，０≦ｙ
≦６］で示される金属ガラス合金に係わる発明について特許出願した（特許文献１１）。
この組成に含まれる式Ｆｅ７４Ｓｉ７．２Ｂ１０．８Ｐ３．２Ｃ０．８Ｍｏ２の粒子材（
実施例３−３）は、ΔＴｘが４８．４Ｋ、Ｂｓ（Ｔ）は１．２８であるが、図９の磁化曲
線に示されるとおり、Ｎｂを１ａｔ％を含有する合金（実施例１−３）に比べて軟磁気特
性はよくなかった。
One FeCrMoGaPCBSi metallic glass alloy shows a greater glass forming ability,
Although it is possible to produce metallic glass alloys up to 4 mm in diameter or thickness with flux melting and water quenching, this method is complex and the Is is low (less than 1T). The inventors of the present invention have so far vigorously developed soft magnetic Fe-based metallic glass alloys (
An alloy having a coercive force of 3.5 to 3.0 A / m and containing 1 at% of Nb has excellent soft magnetic characteristics shown in the magnetization curve shown in FIG. In addition, the inventors have the composition Fe 76-y
{(Si a B b) m (P c C d) n} x M y [M; Nb, Mo, 19 ≦ x ≦ 30,0 ≦ y
A patent application was filed for an invention related to a metallic glass alloy represented by ≦ 6] (Patent Document 11).
Particulate material of the formula Fe 74 Si 7.2 B 10.8 P 3.2 C 0.8 Mo 2 included in this composition (
In Example 3-3), ΔTx is 48.4K and Bs (T) is 1.28, but as shown in the magnetization curve of FIG. 9, an alloy containing 1 at% of Nb (Example 1-3) Compared with), the soft magnetic properties were not good.
軟磁性材料としては、従来、珪素鋼、フェライト、鉄基およびコバルト基非晶質合金薄
帯などが使用されている。これらのうち、鉄基非晶質合金薄帯は、約１．５Ｔの高い飽和
磁化を持つものの、磁歪が大きいために透磁率は数千であり低い。これに対して、コバル
ト基非晶質合金薄帯の透磁率は数万のレベルと高いものの、飽和磁化は１Ｔ以下であり、
飽和磁化と軟磁気特性（透磁率、保磁力、鉄損など）の両方の特性に優れた合金材料の開
発は非常に困難であった。
Conventionally, silicon steel, ferrite, iron-based and cobalt-based amorphous alloy ribbons have been used as soft magnetic materials. Among these, the iron-based amorphous alloy ribbon has a high saturation magnetization of about 1.5 T, but has a large permeability and a low permeability of several thousand. In contrast, the permeability of the cobalt-based amorphous alloy ribbon is as high as several tens of thousands, but the saturation magnetization is 1T or less,
It has been very difficult to develop an alloy material excellent in both saturation magnetization and soft magnetic properties (permeability, coercivity, iron loss, etc.).
また、バルクの非晶質合金である従来のＦｅ−Ｂ−Ｃ系軟磁性金属ガラス合金は、飽和
磁化が小さく、変圧器やモーター用途の要求を満たさない。また、Ｆｅ−Ｂ−Ｃ系軟磁性
金属ガラス合金であって、Ｇａを使用しているものは、コストが高い。鉄濃度の高い鉄・
遷移金属非晶質合金を熱処理してナノメータサイズの微細な結晶を均一に析出させること
により高い飽和磁化と共に優れた軟磁気特性を兼ね備えた軟磁性材料の開発もなされてい
るが、熱処理工程の厳密な制御が必要になり、コストが高い。したがって、実用化を進め
るために、ガラス形成能及び初期透磁力、保磁力、飽和磁化などの軟磁気特性の改善、並
びに、原材料や製造工程のコストの低減が強く求められている。
Moreover, the conventional Fe-B-C type soft magnetic metallic glass alloy which is a bulk amorphous alloy has a small saturation magnetization, and does not satisfy the requirements for transformers and motor applications. Further, an Fe—B—C soft magnetic metal glass alloy using Ga is expensive. Iron with high iron concentration
Soft magnetic materials that combine high saturation magnetization with excellent soft magnetic properties have been developed by heat-treating transition metal amorphous alloys to uniformly precipitate fine crystals of nanometer size. Costly control is required and the cost is high. Therefore, in order to promote practical application, there is a strong demand for improvement of soft magnetic properties such as glass forming ability, initial permeability, coercivity, and saturation magnetization, and reduction of costs of raw materials and manufacturing processes.
そこで、本発明者らは、上述の課題を解決することを目的として種々の合金組成及び元
素の組み合わせの方法について探査した結果、高価な元素Ｇａを含有しないＦｅ79-x
ＭｏxＰ10Ｃ4Ｂ4Ｓｉ3（ｘ＝２〜５ａｔ％）で示されるＦｅ基金属ガラス合金が、
過冷却液体の温度間隔ΔＴｘが４０Ｋ以上であり、保磁力(Ｈｃ)が１．５〜２．１Ａ/ｍ
、飽和磁化（Ｉｓ）が１．１４Ｔ〜１．３９Ｔ、１ｋＨｚ、１Ａ／ｍでの初期透磁率(μ
e) が１８６００〜２５２３０、磁歪（λｓ）が１７．７×１０-6〜２２．７である
ことを見出し、本発明の完成に至った。
Therefore, as a result of exploring various alloy compositions and methods of element combinations for the purpose of solving the above-mentioned problems, the present inventors have found that Fe 79-x not containing an expensive element Ga.
Fe-based metallic glass alloy represented by Mo x P 10 C 4 B 4 Si 3 (x = 2 to 5 at%)
The temperature interval ΔTx of the supercooled liquid is 40K or more, and the coercive force (Hc) is 1.5 to 2.1 A / m.
, Saturation permeability (Is) of 1.14T to 1.39T, 1 kHz, initial permeability at 1 A / m (μ
It was found that e ) was 18600 to 25230 and magnetostriction (λs) was 17.7 × 10 −6 to 22.7, and the present invention was completed.
本発明の金属ガラス合金は、過冷却液体の温度間隔ΔＴｘが大きく、直径又は厚さが１
．５ｍｍ〜４ｍｍで、ガラス相の体積分率が１００％であるものを金型鋳造法によって製
造することができる。
The metallic glass alloy of the present invention has a large temperature interval ΔTx of the supercooled liquid and a diameter or thickness of 1
. A glass phase volume fraction of 5% to 4 mm and 100% can be produced by a die casting method.
図６に、各種の軟磁性材料の飽和磁化と透磁率の関係を本発明の合金と対比して示す。
本発明の金属ガラス合金は、これまでのＦｅ−Ｐ−Ｃ系金属ガラス合金中で最高のＩｓ，
優れた軟磁気特性を有することが理解される。
FIG. 6 shows the relationship between the saturation magnetization and magnetic permeability of various soft magnetic materials in comparison with the alloy of the present invention.
The metallic glass alloy of the present invention has the highest Is, among the conventional Fe-PC-based metallic glass alloys.
It is understood that it has excellent soft magnetic properties.
上記の合金組成において、銅鋳型鋳造法により作製した鋳造棒材について測定したΔＴ
ｘ＝Ｔｘ−Ｔｇの式で表される過冷却液体の温度間隔ΔＴｘは４１Ｋ以上である。また、
換算ガラス化温度Ｔｇ/Ｔｌが０．６００以上である。
In the above alloy composition, ΔT measured for a cast bar produced by a copper mold casting method.
The temperature interval ΔTx of the supercooled liquid expressed by the equation x = Tx−Tg is 41K or more. Also,
The conversion vitrification temperature Tg / Tl is 0.600 or more.
この組成を持つ合金を用いて、銅鋳型鋳造法により作製した金属ガラスは、熱分析を行
う際、明瞭なガラス遷移及び結晶化による発熱が観察され、ガラス形成の臨界厚さ又は直
径の値は１．５ｍｍ以上であり、最大では４ｍｍに達するので、銅鋳型鋳造法によって厚
さ又は直径１．５ｍｍ〜４ｍｍの範囲でガラス相の体積分率が１００％であるバルク金属
ガラス合金を容易に製作できる。
When an alloy having this composition is used for the metal glass produced by the copper mold casting method, a clear glass transition and heat generation due to crystallization are observed during thermal analysis, and the critical thickness or diameter value of the glass formation is Since it is 1.5 mm or more and reaches a maximum of 4 mm, a bulk metallic glass alloy having a glass phase volume fraction of 100% within a thickness or diameter of 1.5 mm to 4 mm can be easily manufactured by a copper mold casting method. it can.
以上説明したように、本発明のＦｅ基金属ガラス合金は、ガラス形成能に優れ、ガラス
形成の臨界厚さ又は直径が１．５ｍｍ以上であり、最大では直径又は厚さ４ｍｍの値を有
する。従来のＦｅ−Ｐ−Ｃ系バルク金属ガラス合金には不可欠のＧａ元素を含有しないに
もかかわらず、高いガラス形成能を示すとともに、高飽和磁化と優れた軟磁気特性を示す
材料の開発に成功した。
As described above, the Fe-based metallic glass alloy of the present invention is excellent in glass forming ability, has a critical thickness or diameter of glass formation of 1.5 mm or more, and has a maximum diameter or thickness of 4 mm. Succeeded in developing a material that exhibits high glass-forming ability, high saturation magnetization, and excellent soft magnetic properties, despite the fact that it does not contain the essential Ga element in conventional Fe-PC-C bulk metal glass alloys did.
次に、本発明の実施の形態を説明する。本発明の上記合金組成は、基本的に下記６種の
元素を構成要素としている。Ｆｅ：鉄、Ｍｏ：モリブデン、Ｐ；燐、Ｃ；炭素，Ｂ：ホウ
素、Ｓｉ：けい素。そして、式Ｆｅ７９−ｘＭｏｘＰ１０Ｃ４Ｂ４Ｓｉ３（ｘ＝２〜５ａ
ｔ％）で示される組成を有する。
Next, an embodiment of the present invention will be described. The above alloy composition of the present invention basically comprises the following six elements. Fe: iron, Mo: molybdenum, P: phosphorus, C: carbon, B: boron, Si: silicon. And the formula Fe 79-x Mo x P 10 C 4 B 4 Si 3 (x = 2-5a
t%).
本発明のＦｅ基金属ガラス合金において、主成分であるＦｅは、本発明の高飽和磁化の
金属ガラス合金の基となる元素である。本発明のＦｅ基金属ガラス合金中のＦｅ含有量は
７４〜７７ａｔ％と高く、大きな飽和磁化が得られる。
In the Fe-based metallic glass alloy of the present invention, Fe, which is the main component, is an element that forms the basis of the highly saturated magnetization metallic glass alloy of the present invention. The Fe content in the Fe-based metallic glass alloy of the present invention is as high as 74 to 77 at%, and a large saturation magnetization is obtained.
本発明の上記合金組成において、半金属元素Ｐ，Ｃ，Ｂ，Ｓｉは、アモルファス相の形
成を担う元素であり、安定なアモルファス構造を得るために重要である。従来のＦｅ−Ｂ
−Ｃ系金属ガラス合金では、ガラス形成能を高めるためには、Ｓｉと組み合わせて、１０
ａｔ％程度以上の高濃度にＢを含有させる必要があった。Ｆｅ−Ｐ−Ｃ系金属ガラス合金
では、ＦｅとＰの間では、Ｆｅの含有量が約８０at％の組成で一つの共晶点が存在してお
り、この共晶点近傍での組成はガラス形成能が高い。また、ガラス形成能の向上には、安
定な過冷却液体が必要である。そのため、原子サイズの異なったＣ，Ｂ，Ｓｉを添加する
ことにより安定なアモルファス構造が得られ、ガラス形成能が向上する。
In the above alloy composition of the present invention, the metalloid elements P, C, B, and Si are elements responsible for forming an amorphous phase, and are important for obtaining a stable amorphous structure. Conventional Fe-B
In the case of the -C-based metallic glass alloy, in order to increase the glass forming ability, in combination with Si, 10
It was necessary to contain B at a high concentration of about at% or more. In the Fe-PC-C-based metallic glass alloy, there is one eutectic point between Fe and P with a composition of Fe content of about 80 at%, and the composition near this eutectic point is glass. High ability to form. Moreover, a stable supercooled liquid is required for improving the glass forming ability. Therefore, by adding C, B, and Si having different atomic sizes, a stable amorphous structure is obtained, and the glass forming ability is improved.
本発明の合金では、半金属元素Ｐ，Ｃ，Ｂ，Ｓｉをともに特定の含有量で含有させるこ
とにより、合計の含有量が少なくてもガラス形成能が優れることを見出した。これらの半
金属元素の合計の含有量は約２０at％は必要である。これらの半金属元素が規定の量より
多くなるにつれ、共晶点から離れるので、ガラス形成能は低下し、飽和磁化は低下する。
また、規定の量より少なくなると、飽和磁化はやや大きくなる傾向があるが、ガラス形成
能が急激に低下する。Ｐ元素は、合金全体を一つの共晶点に持っていく役割をする。
In the alloy of the present invention, it has been found that the glass forming ability is excellent even when the total content is small by containing the metalloid elements P, C, B, and Si at a specific content. The total content of these metalloid elements is required to be about 20 at%. As the amount of these metalloid elements exceeds the specified amount, the glass forming ability is lowered and the saturation magnetization is lowered because it is away from the eutectic point.
On the other hand, when the amount is less than the specified amount, the saturation magnetization tends to be slightly increased, but the glass forming ability is rapidly lowered. The element P plays a role of bringing the entire alloy into one eutectic point.
Ｆｅの２〜５ａｔ％をＭｏで置換することによりΔＴｘをかなり拡大し、ガラス形成能
を大幅に増加させる。Ｍｏの添加は、Ｃ，Ｂ，Ｓｉの添加で共晶点からずれた組成を共晶
点に戻す役割をする。ΔＴｘの増大は、結晶化の遅滞による。Ｍｏを含有しない場合は準
安定相のＦｅ２３（Ｂ，Ｃ）６相が析出するが、Ｆｅをわずか１ａｔ％のＭｏで置換する
ことにより準安定相は析出しなくなる。少量のＭｏで合金化することによって、ＳｉとＭ
ｏの間の大きな負の値を持つ混合エンタルピーが準安定（Ｆｅ，Ｍｏ）２３（Ｂ，Ｃ）６
相の形成の困難さを大きくするので準安定相の析出は強く阻止されると考えられる。加え
て、大きな（Ｆｅ及びＭｏ）及び小さな（Ｂ及びＣ）原子は、アモルファス構造中に補強
されたバックボーンを形成し、また結晶化を抑制すると思われる。これらの二つの作用に
より、過冷却液体の安定性を増加させる。一方、これらの合金は共晶か、それに近い組成
である。
By substituting 2 to 5 at% of Fe with Mo, ΔTx is considerably enlarged and the glass forming ability is greatly increased. The addition of Mo serves to return the composition shifted from the eutectic point to the eutectic point by the addition of C, B, and Si. The increase in ΔTx is due to crystallization delay. When Mo is not contained, the metastable phase Fe 23 (B, C) 6 phase is precipitated, but the metastable phase is not precipitated by substituting Fe with only 1 at% of Mo. By alloying with a small amount of Mo, Si and M
The mixed enthalpy with a large negative value between o is metastable (Fe, Mo) 23 (B, C) 6
Precipitation of the metastable phase is thought to be strongly prevented because it increases the difficulty of phase formation. In addition, large (Fe and Mo) and small (B and C) atoms appear to form a reinforced backbone in the amorphous structure and suppress crystallization. These two actions increase the stability of the supercooled liquid. On the other hand, these alloys are eutectic or have a composition close to that.
本発明の上記合金組成において、組成範囲からのずれにより、ガラス形成能が劣り、溶
湯から凝固過程にかけて、結晶核が生成・成長し、ガラス相に結晶相が混在した組織にな
る。また、この組成範囲から大きく離れると、ガラス相が得られず、結晶相となる。
In the above alloy composition of the present invention, the glass forming ability is inferior due to the deviation from the composition range, crystal nuclei are generated and grown from the molten metal to the solidification process, and the glass phase has a mixed crystal phase. Moreover, if it leaves | separates greatly from this composition range, a glass phase will not be obtained but it will become a crystal phase.
本発明の上記合金組成において、ガラス形成能が高いため、銅鋳型鋳造すると直径又は
厚さが４ｍｍまでのガラス相の体積分率が１００％の金属ガラス合金の棒材又は板材が作
製できるが、同様な冷却速度で、回転水中紡糸法により、直径０．５５ｍｍまでの細線、
アトマイズ法により、直径０．６ｍｍまでの粒子の金属ガラスを作製できる。
In the above alloy composition of the present invention, since the glass forming ability is high, when a copper mold is cast, a rod or plate of a metal glass alloy with a volume fraction of the glass phase up to 4 mm in diameter or thickness can be produced. A thin wire up to a diameter of 0.55 mm by a rotating underwater spinning method at a similar cooling rate,
By the atomizing method, metallic glass having a particle diameter of up to 0.6 mm can be produced.
本発明の合金は、実施例に示すように、Ｍｏの含有量が２〜５ａｔ％の範囲で、１ｋＨ
ｚ、１Ａ／ｍでの初期透磁率(μｅ) が１８６００〜２５２３０、保磁力(Ｈｃ)が１．５
〜２．１Ａ／ｍ、飽和磁化（Ｉｓ）が１．１４〜１．３９Ｔ、の極めて優れた軟磁気特性
を持つＦｅ基金属ガラス合金である。さらに、Ｍｏの含有量が３〜４ａｔ％の範囲では、
初期透磁率(μｅ) が２４６１０〜２５２３０、保磁力(Ｈｃ)が１．５〜１．７Ａ／ｍ、
飽和磁化（Ｉｓ）が１．２７〜１．３２Ｔとなり、より優れた軟磁気特性が得られる。
As shown in the examples, the alloy of the present invention has a Mo content in the range of 2 to 5 at%.
z Initial permeability (μ e ) at 1 A / m is 18600-25230, coercive force (Hc) is 1.5
It is an Fe-based metallic glass alloy having extremely excellent soft magnetic properties of ˜2.1 A / m and saturation magnetization (Is) of 1.14 to 1.39 T. Furthermore, in the range where the Mo content is 3 to 4 at%,
Initial magnetic permeability (μ e ) is 24610-25230, coercive force (Hc) is 1.5-1.7 A / m,
The saturation magnetization (Is) is 1.27 to 1.32T, and more excellent soft magnetic characteristics can be obtained.
表１に示すＡ０〜Ａ５の合金材料を調製し、銅鋳型鋳造法を実施し、バルク合金を得た
。図５に、銅鋳型鋳造法により直径１〜４ｍｍの合金試料を作製するのに用いた装置を側
面から見た概略構成を示す。Ａ０〜Ａ５の各合金組成は式Ｆｅ７９−ｘＭｏｘＰ１０Ｃ４
Ｂ４Ｓｉ３において、ｘ＝０（Ａ０），ｘ＝１（Ａ１），ｘ＝２（Ａ２），ｘ＝３（Ａ３
），ｘ＝４（Ａ４），ｘ＝５（Ａ５）、ｘ＝６（Ａ６）とした。
Alloy materials of A0 to A5 shown in Table 1 were prepared, and a copper mold casting method was performed to obtain a bulk alloy. FIG. 5 shows a schematic configuration of an apparatus used for producing an alloy sample having a diameter of 1 to 4 mm by a copper mold casting method as viewed from the side. Each alloy composition of A0 to A5 has the formula Fe 79-x Mo x P 10 C 4
In B 4 Si 3 , x = 0 (A0), x = 1 (A1), x = 2 (A2), x = 3 (A3
), X = 4 (A4), x = 5 (A5), and x = 6 (A6).
純鉄、純Ｍｏ，Ｓｉメタロイド、Ｆｅ−Ｐプレアロイ、Ｆｅ−Ｃプレアロイ、純Ｂ結晶
の混合物を高純度Ａｒ雰囲気中で誘導加熱溶融することにより合金インゴットを製造した
。
An alloy ingot was manufactured by induction heating and melting a mixture of pure iron, pure Mo, Si metalloid, Fe—P prealloy, Fe—C prealloy, and pure B crystal in a high purity Ar atmosphere.
この合金インゴットを先端に小孔（孔径0.5〜4mm）を有する石英管３に充填し、高周波
発生コイル４により加熱溶融した。その後、その石英管３を垂直な孔５を鋳込み空間とし
て設けた銅製鋳型６の直上に設置した。次いで、石英管３内の溶融金属１をアルゴンガス
の加圧（0.1〜1.0 Kg/cm2）により石英管３の小孔２から噴出し、銅製鋳型６の孔に注入
してそのまま放置して凝固させて直径４ｍｍまでの長さ４０ｍｍの円柱状鋳造棒を製造し
た。
This alloy ingot was filled in a
表１に、試料Ａ０〜Ａ５の示差走査熱量計を用いて測定したガラス遷移温度（Ｔｇ）、
ΔＴｘ＝Ｔｘ−Ｔｇ（Ｔｘは結晶化開始温度）、Ｔｇ/Ｔｌを示す。また、Ｉｓ，Ｈｃ，
１ｋＨｚでの初期透磁率（μｅ）を、それぞれ、４００ｋＡ／ｍの磁場を印加した振動試
料型マグネトメーター、８００Ａ／ｍの磁場でのＢ−Ｈループトレーサー、１Ａ／ｍの磁
場でのインピーダンスアナライザーにより測定した。磁歪（λｓ）は３端子キャパシタン
ス法により測定した。
In Table 1, the glass transition temperature (Tg) measured using the differential scanning calorimeter of samples A0 to A5,
ΔTx = Tx−Tg (Tx is the crystallization start temperature), Tg / Tl. Also, Is, Hc,
An initial permeability (μ e ) at 1 kHz, a vibrating sample magnetometer applied with a magnetic field of 400 kA / m, a BH loop tracer with a magnetic field of 800 A / m, and an impedance analyzer with a magnetic field of 1 A / m, respectively. It was measured by. Magnetostriction (λs) was measured by the three-terminal capacitance method.
図１に、Ｆｅ７９−ｘＭｏｘＰ１０Ｃ４Ｂ４Ｓｉ３（ｘ＝０〜６ａｔ％）のＤＳＣ曲線
を示す。Ｍｏの含有量が０から４ａｔ％に増加するにつれてＴｇとΔＴｘは７４０から７
５２Ｋ、３４から４７Ｋへそれぞれ増加する。Ａ０合金の結晶化は、３つの発熱段階で生
じ、Ｐ１，Ｐ２，Ｐ３の印を付した３つの対応する発熱ピークは接近している。しかしな
がら、結晶化は、Ｆｅを１〜４ａｔ％のＭｏで置換すると２つの段階を通して生じ、Ａ３
とＡ４合金は主の発熱ピークに肩(shoulder)を示すが、２つの発熱ピーク間の温度間隔は
Ｍｏ含有量が増えるにつれて増加する。
FIG. 1 shows a DSC curve of Fe 79-x Mo x P 10 C 4 B 4 Si 3 (x = 0 to 6 at%). Tg and ΔTx are increased from 740 to 7 as the Mo content increases from 0 to 4 at%.
Increase from 52K, 34 to 47K, respectively. Crystallization of the A0 alloy occurs in three exothermic stages, and the three corresponding exothermic peaks marked P1, P2, P3 are close. However, crystallization occurs through two stages when Fe is replaced with 1-4 at% Mo, and A3
And the A4 alloy show shoulders in the main exothermic peak, but the temperature interval between the two exothermic peaks increases as the Mo content increases.
Ｍｏ含有量が５ａｔ％及び６ａｔ％にさらに増加すると、肩は、面心立方晶（Ｆｅ、
Ｍｏ）２３（Ｂ，Ｃ）６相の析出により発熱ピークになる。特に、Ａ６合金については、
ピークＰ１は、大きく、結晶化は、ΔＴの大幅な低下を伴って、再度、３つの明白な発熱
段階を通って生じる。それゆえに、過冷却液体（ＳＬ）の熱的安定性はＭｏ含有量が４ａ
ｔ％へ増加するにつれて増加し、さらにＭｏ含有量が増加すると減少が始まると推測され
る。
When the Mo content is further increased to 5 at% and 6 at%, the shoulder is face-centered cubic (Fe,
Mo) 23 (B, C) Exothermic peak due to precipitation of 6 phases. Especially for the A6 alloy,
Peak P1 is large and crystallization occurs again through three distinct exothermic stages, with a significant drop in ΔT. Therefore, the thermal stability of the supercooled liquid (SL) has a Mo content of 4a.
It increases with increasing to t%, and it is estimated that the decrease starts when the Mo content further increases.
図２に、Ｆｅ７９−ｘＭｏｘＰ１０Ｃ４Ｂ４Ｓｉ３（ｘ＝０〜５ａｔ％）のＤＴＡ曲線
を示す。Ａ０合金については、Ｐｅｎｄｏ１及びＰｅｎｄｏ２の符号を付した２つの吸熱
ピークが加熱曲線上に見える。これは該組成が共晶点の近くに存在していないことを示唆
する。Ｍｏ含有量が１から４ａｔ％へ増加するにつれてピークＰｅｎｄｏ１の強度は、増
加するが、ピークＰｅｎｄｏ２の強度は次第に低下する。こうして、Ｍｏが２，３，４ａ
ｔ％にそれぞれ増加すると、事実上たった一つのピークが残り、Ｍｏ含有量が４ａｔ％に
増加すると共晶点に接近することを示している。Ｍｏ含有量がさらに５ａｔ％に増加する
と、２つの吸熱ピークが再度現れるので、Ｍｏ含有量が５ａｔ％に増加すると合金の組成
は共晶点から離れ始めることを示唆する。
FIG. 2 shows a DTA curve of Fe 79-x Mo x P 10 C 4 B 4 Si 3 (x = 0 to 5 at%). For the A0 alloy, two endothermic peaks labeled P endo1 and P endo2 are visible on the heating curve. This suggests that the composition does not exist near the eutectic point. As the Mo content increases from 1 to 4 at%, the intensity of the peak P endo1 increases, but the intensity of the peak P endo2 gradually decreases. Thus, Mo becomes 2, 3, 4a.
As each increase to t%, virtually only one peak remains, indicating that the eutectic point is approached when the Mo content is increased to 4 at%. When the Mo content is further increased to 5 at%, two endothermic peaks reappear, suggesting that when the Mo content is increased to 5 at%, the composition of the alloy begins to move away from the eutectic point.
加えて、冷却曲線に示されるように、Ｍｏ含有量が１から４ａｔ％に増加するにつれて
Ｔｌは１２７０から１２２６Ｋに低下し、Ｍｏ含有量がさらに５ａｔ％に増加するにつれ
て再度１２６５Ｋに高まる。Ａ４合金は、２つの発熱ピークを示すが、他のＭｏ含有合金
は３以上の発熱ピークを示すので、Ａ４合金の凝固挙動は他の合金よりも単純であること
を示している。それゆえ、Ａ２，Ａ３，Ａ４合金は共晶点の近くにあり、Ａ４合金はこれ
らの３つの合金の中では最も共晶点に近いと考えられる。
In addition, as shown in the cooling curve, Tl decreases from 1270 to 1226K as the Mo content increases from 1 to 4 at% and increases again to 1265K as the Mo content increases further to 5 at%. The A4 alloy shows two exothermic peaks, but other Mo-containing alloys show three or more exothermic peaks, indicating that the solidification behavior of the A4 alloy is simpler than other alloys. Therefore, the A2, A3, and A4 alloys are close to the eutectic point, and the A4 alloy is considered to be the closest to the eutectic point among these three alloys.
さらに、換算ガラス化温度（Ｔｇ／Ｔｌ）は０．５８６〜０．６１３の間にある。それ
ゆえ、ＤＳＣ及びＤＴＡ測定からこのＦｅＰＣ基金属ガラス合金は高いガラス形成能を示
す結果となると考えられる。金属ガラス合金棒の臨界直径は、Ａ０，Ａ１，Ａ２，Ａ３，
Ａ４，及びＡ５のそれぞれについて、１,１．５，２．５，３．５，４，及び３ｍｍであ
る。図３に、これらの鋳造棒のＸＲＤパターンを示す。結晶のピークを伴わない広いピー
クのみがこれらの鋳造棒全てに見ら、４ｍｍまでの直径でガラス相の形成が示唆される。
Furthermore, the conversion vitrification temperature (Tg / Tl) is between 0.586 and 0.613. Therefore, it can be considered from DSC and DTA measurements that this FePC-based metallic glass alloy exhibits a high glass forming ability. The critical diameter of metallic glass alloy rods is A0, A1, A2, A3
For each of A4 and A5, it is 1, 1.5, 2.5, 3.5, 4, and 3 mm. FIG. 3 shows the XRD patterns of these cast bars. Only a broad peak with no crystal peak is seen in all of these cast bars, suggesting the formation of a glass phase with diameters up to 4 mm.
上記の表１にＡ０〜Ａ５合金の最大直径（Ｄmax;ｍｍ）、熱安定性、磁気特性を示す。
Ｍｏ含有量が０から５ａｔ％に増加するにつれて、Ｆｅ含有量の低下により飽和磁化（Ｉ
ｓ）が１．５３から１．１４Ｔに低下するけれども、Ｆｅ含有量の合計が７４ａｔ％より
多いので、このガラス合金のＩｓは、どの他のＦｅ−Ｐ−Ｃ系金属ガラス合金よりも高い
。最大のガラス形成能を有するＡ３及びＡ４金属ガラス合金は、最良の軟磁気特性を示す
。この理由は、結晶核を全く含まない高いレベルの同質性(homogeneity)を持つガラス構
造の形成による。実際、Ａ３及びＡ４合金は、約１５×１０−６の最低の磁歪（λｓ）を
示す。結果として、１．３２及び１．２７Ｔのより高いＩｓに加えて、非常に大きい初期
透磁率（μｅ）を持つ優れた軟磁気特性がＡ３及びＡ４ガラス合金について得られた。
Table 1 shows the maximum diameter (Dmax; mm), thermal stability, and magnetic properties of the A0 to A5 alloys.
As the Mo content increases from 0 to 5 at%, the saturation magnetization (I
Although s) drops from 1.53 to 1.14 T, the total Fe content is greater than 74 at%, so the Is of this glass alloy is higher than any other Fe-PC-based metallic glass alloy. A3 and A4 metallic glass alloys with maximum glass forming ability exhibit the best soft magnetic properties. The reason for this is due to the formation of a glass structure with a high level of homogeneity that does not contain any crystal nuclei. Indeed, A3 and A4 alloys exhibit a minimum magnetostriction (λs) of about 15 × 10 −6 . As a result, excellent soft magnetic properties with very high initial magnetic permeability (μ e ) in addition to the higher Is of 1.32 and 1.27 T were obtained for A3 and A4 glass alloys.
図４には、比較のためにメルトスピン法で作製した金属ガラス合金リボンのＸＲＤパタ
ーンも示している。準安定（Ｆｅ，Ｍｏ）２３（Ｂ，Ｃ）６相のＸＲＤパターン５ｍｍ径
の鋳造棒のＸＲＤパターンに重ねて示しているとおり、（Ｆｅ，Ｍｏ）２３（Ｂ，Ｃ）６
相が５ｍｍ径のロッドのガラス相から析出していることが分かる。それゆえ、準安定（Ｆ
ｅ，Ｍｏ）２３（Ｂ，Ｃ）６相は事実、ガラス相の形成と競合する主相であることが確認
される。図７に、Ａ２〜Ａ５合金の磁化曲線を示す。本発明のＦｅ基金属ガラス合金は、
非常に大きい初期透磁率が得られることが分かる。
FIG. 4 also shows an XRD pattern of a metallic glass alloy ribbon manufactured by a melt spin method for comparison. Metastable (Fe, Mo) 23 (B, C) 6- phase XRD pattern (Fe, Mo) 23 (B, C) 6 as shown superimposed on the XRD pattern of a 5 mm diameter casting rod
It can be seen that the phase is precipitated from the glass phase of the 5 mm diameter rod. Therefore, metastable (F
e, Mo) 23 (B, C) The six phases are indeed confirmed to be the main phase competing with the formation of the glass phase. FIG. 7 shows the magnetization curves of the A2 to A5 alloys. The Fe-based metallic glass alloy of the present invention is
It can be seen that a very large initial permeability is obtained.
本発明のＦｅ基金属ガラス合金は 銅鋳型鋳造法により製造された棒材又は板材を提供
することができ、高い飽和磁化と大きい初期透磁率を有しているので、電力変圧器のコア
材やモータコア材などの高透磁率磁心材料として特に有用であり、その他、スイッチング
電源用トランス。チョークコイル、ノイズフイルタなどの磁心材料、電磁シールド材、磁
気センサ、電流センサなど、幅広い応用が期待される。
る。
The Fe-based metallic glass alloy of the present invention can provide a bar or plate manufactured by a copper mold casting method, and has high saturation magnetization and large initial permeability. It is particularly useful as a high-permeability magnetic core material such as a motor core material. A wide range of applications such as magnetic core materials such as choke coils and noise filters, electromagnetic shielding materials, magnetic sensors, and current sensors are expected.
The
Claims (2)
過冷却液体の温度間隔ΔＴｘが４０Ｋ以上、直径又は厚さが１．５ｍｍ〜４ｍｍでガラス
相の体積分率が１００％であり、保磁力(Ｈｃ)が１．５〜２．１Ａ/ｍ、飽和磁化（Ｉｓ
）が１．１４Ｔ〜１．３９Ｔ、１ｋＨｚ、１Ａ／ｍでの初期透磁率(μe) が１８６００
〜２５２３０であることを特徴とする軟磁性Ｆｅ基金属ガラス合金。 The composition is represented by the formula; Fe 79-x Mo x P 10 C 4 B 4 Si 3 (x = 2 to 5 at%)
The temperature interval ΔTx of the supercooled liquid is 40K or more, the diameter or thickness is 1.5 mm to 4 mm, the volume fraction of the glass phase is 100%, the coercive force (Hc) is 1.5 to 2.1 A / m, Saturation magnetization (Is
) Is 1.14T to 1.39T, 1 kHz, initial magnetic permeability (μ e ) at 1 A / m is 18600
A soft magnetic Fe-based metallic glass alloy characterized by being 25230 .
なることを特徴とする磁心材料。 A magnetic core material comprising a bar or plate material of an Fe-based metallic glass alloy according to claim 1 manufactured by a copper mold casting method.
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| CN103492108B (en) | 2011-04-28 | 2015-09-09 | 国立大学法人东北大学 | The manufacture method of glassy metal nano wire, the glassy metal nano wire manufactured by this manufacture method and the catalyst containing glassy metal nano wire |
| WO2013087627A1 (en) * | 2011-12-12 | 2013-06-20 | Ocas Onderzoekscentrum Voor Aanwending Van Staal N.V. | Fe-based soft magnetic glassy alloy material |
| CN102912257A (en) * | 2012-10-19 | 2013-02-06 | 张家港市清大星源微晶有限公司 | Microcrystalline material |
| CN102875024A (en) * | 2012-10-19 | 2013-01-16 | 张家港市清大星源微晶有限公司 | Microcrystalline material with high magnetic inductivity |
| EP2759614B1 (en) * | 2013-01-25 | 2019-01-02 | ThyssenKrupp Steel Europe AG | Method for generating a flat steel product with an amorphous, semi-amorphous or fine crystalline structure and flat steel product with such structures |
| JP6347606B2 (en) * | 2013-12-27 | 2018-06-27 | 井上 明久 | High magnetic flux density soft magnetic iron-based amorphous alloy with high ductility and high workability |
| CN109503143A (en) * | 2018-12-18 | 2019-03-22 | 横店集团东磁股份有限公司 | It is a kind of curtain coating raw cook, and preparation method thereof and with its prepare magnetic sheet |
| JP6741108B1 (en) * | 2019-03-26 | 2020-08-19 | Tdk株式会社 | Soft magnetic alloys and magnetic parts |
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| JP3929327B2 (en) * | 2002-03-01 | 2007-06-13 | 独立行政法人科学技術振興機構 | Soft magnetic metallic glass alloy |
| JP4358016B2 (en) * | 2004-03-31 | 2009-11-04 | 明久 井上 | Iron-based metallic glass alloy |
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