JP2015127436A5 - - Google Patents
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- JP2015127436A5 JP2015127436A5 JP2013272759A JP2013272759A JP2015127436A5 JP 2015127436 A5 JP2015127436 A5 JP 2015127436A5 JP 2013272759 A JP2013272759 A JP 2013272759A JP 2013272759 A JP2013272759 A JP 2013272759A JP 2015127436 A5 JP2015127436 A5 JP 2015127436A5
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 114
- 229910052742 iron Inorganic materials 0.000 claims description 50
- 239000000956 alloy Substances 0.000 claims description 38
- 229910045601 alloy Inorganic materials 0.000 claims description 37
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 36
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 25
- 230000004907 flux Effects 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 238000005452 bending Methods 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 230000037248 Effective permeability Effects 0.000 claims description 4
- 238000005275 alloying Methods 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 238000007712 rapid solidification Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 description 14
- 238000002425 crystallisation Methods 0.000 description 7
- 230000005712 crystallization Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 229910000676 Si alloy Inorganic materials 0.000 description 5
- 229910018540 Si C Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000004429 atoms Chemical group 0.000 description 3
- 230000001131 transforming Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 2
- 230000001965 increased Effects 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000005300 metallic glass Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052803 cobalt Inorganic materials 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052904 quartz Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 239000000700 tracer Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Description
これまでに報告されている代表的な鉄基アモルファス合金およびガラス合金の組成と飽和磁束密度は、アライドケミカル社が開発して、産業化を果たしたメタルグラスでは、Ｆｅ78Ｓｉ9Ｂ13（原子％）での１．５４Ｔである。 This saturation magnetic flux density and composition of a typical iron-based amorphous alloy and glass alloys that have been reported so far, been developed by Allied Chemical Corporation, in Metall glass played industrialization, Fe 78 Si 9 B 13 ( 1.54T in atomic%).
ところで、このような鉄基軟磁性アモルファス合金としては、上述したように、従来より多くの提案がなされているが、例えば、特許文献１〜５に開示された鉄基アモルファス合金等も挙げることができる。
特許文献１には、鉄、ホウ素、及びケイ素からなり、Ｆｅ濃度が７９．５〜８０．５原子％である非晶質Ｆｅ−Ｂ−Ｓｉ合金が開示されている。この非晶質Ｆｅ−Ｂ−Ｓｉ合金は、従来の合金に比較して大きい飽和磁気誘導、高い結晶化温度、低いコアロス、低い励磁電力、良好な延性を備えることが開示されている。
また、特許文献２には、板厚が厚く、かつ、靭性に優れた高靭性非晶質合金薄帯が開示され、具体的には、Ｆｅ濃度が８０．５原子％である非晶質Ｆｅ−Ｂ−Ｓｉ−Ｃ合金であり、合金成分としては、Ｆｅ，Ｃｏ，Ｎｉ等の遷移金属と、Ｂ、Ｓｉ、Ｃ、Ｐなどの半金属の一種または二種以上からなることが開示されている。
Incidentally, as such iron-based soft magnetic amorphous alloy, as described above, many proposals have hitherto been made, for example, also elevation gel iron-based amorphous alloys disclosed in Patent Documents 1 to 5 be able to.
Patent Document 1 discloses an amorphous Fe—B—Si alloy made of iron, boron, and silicon and having an Fe concentration of 79.5 to 80.5 atomic%. It is disclosed that this amorphous Fe—B—Si alloy has a large saturation magnetic induction, a high crystallization temperature, a low core loss, a low excitation power, and a good ductility as compared with a conventional alloy.
Patent Document 2 discloses a high toughness amorphous alloy ribbon having a large plate thickness and excellent toughness. Specifically, an amorphous Fe having an Fe concentration of 80.5 atomic% is disclosed. -B-Si-C alloy, and the alloy component is disclosed to be composed of one or more of transition metals such as Fe, Co, Ni, and semimetals such as B, Si, C, and P. Yes.
また、特許文献３には、鉄、ホウ素、ケイ素及び炭素からなり、Ｆｅ濃度が７７〜８０原子％である非晶質Ｆｅ−Ｂ−Ｓｉ−Ｃ合金が開示されている。この非晶質Ｆｅ−Ｂ−Ｓｉ−Ｃ合金は、従来の合金に比較して、大きい飽和磁気誘導、高いキューリー温度、高い結晶化温度、線周波数での低い鉄損と低い励磁電力の組み合わせを示し、そして電力配電網用の変圧器の磁心への利用に特に適していることが開示されている。
また、特許文献４には、鉄、ホウ素、及びケイ素からなり、Ｆｅ濃度が８１．３〜８１．７原子％である非晶質Ｆｅ−Ｂ−Ｓｉ合金が開示されている。この非晶質Ｆｅ−Ｂ−Ｓｉ合金は、従来の合金に比較して、磁気特性及び物理特性の特別な組み合わせを備えることが開示されている。
また、特許文献５には、鉄、ケイ素、ホウ素、炭素及びリンからなり、Ｆｅ濃度が７８〜８６原子％、Ｓｉ濃度が２原子％以上４原子％未満、Ｂ濃度が２〜１５原子％、Ｃ濃度が０．０２〜４原子％、Ｐ濃度が１〜１４原子％である鉄基非晶質合金薄帯が開示されている。この鉄基非晶質合金薄帯は、従来の鉄基非晶質合金に比較して、磁気特性及び物理特性の特別な組み合わせを備えることが開示されている。
Patent Document 3 discloses an amorphous Fe—B—Si—C alloy made of iron, boron, silicon and carbon and having an Fe concentration of 77 to 80 atomic%. This amorphous Fe-B-Si-C alloy has a combination of large saturation magnetic induction, high Curie temperature, high crystallization temperature, low iron loss at line frequency and low excitation power compared to conventional alloys. And disclosed as being particularly suitable for use in the core of a transformer for a power distribution network.
Patent Document 4 includes iron, boron, and silicon, and the Fe concentration is 81. 3 to 81.7 amorphous Fe-B-Si alloys is atomic% is disclosed. This amorphous Fe-B-Si alloy is disclosed to have a special combination of magnetic and physical properties compared to conventional alloys.
Patent Document 5 includes iron, silicon, boron, carbon, and phosphorus, Fe concentration is 78 to 86 atomic%, Si concentration is 2 atomic% or more and less than 4 atomic%, B concentration is 2 to 15 atomic%, An iron-based amorphous alloy ribbon having a C concentration of 0.02 to 4 atom% and a P concentration of 1 to 14 atom% is disclosed. It is disclosed that this iron-based amorphous alloy ribbon has a special combination of magnetic and physical properties compared to conventional iron-based amorphous alloys.
また、特許文献３には、４成分系の非晶質Ｆｅ−Ｂ−Ｓｉ−Ｃ合金が開示されているが、Ｆｅ濃度が７７〜８０原子％と低く、十分に高濃度で無いと言う課題があった。
また、特許文献４に開示の非晶質Ｆｅ−Ｂ−Ｓｉ合金は、３成分系であり、特許文献１に開示の非晶質合金と同様に、４成分系以上の多成分系アモルファス合金では無いし、特許文献１に開示の非晶質合金より、Ｆｅ濃度が８１．３〜８１．７原子％と高いが、まだ不十分であると言う課題があった。
また、特許文献５には、５成分系のＦｅ−Ｂ−Ｓｉ−Ｐ−Ｃ鉄基非晶質合金薄帯が開示されているが、これらの５成分の組成比率が十分に検討されていないために、飽和磁束密度が最大１．５２であり、十分に高い飽和磁束密度を達成できないと言う課題があった。
Patent Document 3 discloses a quaternary amorphous Fe—B—Si—C alloy, but the problem is that the Fe concentration is as low as 77 to 80 atomic% and is not sufficiently high. was there.
In addition, the amorphous Fe—B—Si alloy disclosed in Patent Document 4 is a ternary system, and like the amorphous alloy disclosed in Patent Document 1, a multi-component amorphous alloy having four or more components is used. There is no Fe concentration of 81.% from the amorphous alloy disclosed in Patent Document 1. Although it was as high as 3 to 81.7 atomic%, there was a problem that it was still insufficient.
Patent Document 5 discloses a five-component Fe—B—Si—P—C iron-based amorphous alloy ribbon, but the composition ratio of these five components has not been sufficiently studied. Therefore, the saturation magnetic flux density is 1.52 at maximum, and there is a problem that a sufficiently high saturation magnetic flux density cannot be achieved.
上記目的を達成するために、本発明者らは、鉄濃度が８１ａｔ％以上のＦｅ８１−８７（Ｂ，Ｃ）ｘ（Ｐ，Ｓｉ）ｙ（ｘ＋ｙ＝１３−１９ａｔ％）組成域で、かなり大きな単位胞（３２原子数）をもつ正方晶構造のＦｅ3（Ｂ，Ｐ）相が非平衡相で存在できることに注目し、この相を基本とした鉄基多成分合金に注目した急冷アモルファス合金の作製と特性について鋭意研究を行い、本発明に至ったものである。
即ち、本発明の高延性・高加工性を持つ高磁束密度軟磁性鉄基非晶質合金は、合金元素として、鉄、ホウ素、硅素及び燐を含有し、合金組成がＦｅaＢbＳｉｃＰｄで表わされ、ａ，ｂ，ｃ，ｄが原子パーセントである時、ａ，ｂ，ｃ，及びｄは、下記式 ８１≦ａ≦８７、７≦ｂ≦１０、０＜ｄ≦ｃ＜ｃ＋ｄ＜ｂ、ａ＋ｂ＋ｃ＋ｄ≦１００を満足し、飽和磁束密度が１．６０Ｔ以上であることを特徴とする。
In order to achieve the above object, the inventors of the present invention have found that the Fe 81-87 (B, C) x (P, Si) y (x + y = 13-19 at%) composition range having an iron concentration of 81 at% or more Focusing on the fact that tetragonal Fe 3 (B, P) phase with large unit cell (32 atoms) can exist in non-equilibrium phase, quenching amorphous alloy focusing on iron-based multicomponent alloy based on this phase As a result, the present inventors have conducted extensive research on the production and properties of the present invention and have arrived at the present invention.
That is, high magnetic flux density soft magnetic iron-based amorphous alloy having a high ductility and high workability of the present invention, as an alloying element, iron, boron, contain silicon and phosphorus, the alloy composition is Fe a B b Si c When represented by P d and a, b, c and d are atomic percent, a, b, c and d are represented by the following formulas 81 ≦ a ≦ 87, 7 ≦ b ≦ 10, 0 <d ≦ c. <C + d <b, a + b + c + d ≦ 100 is satisfied, and the saturation magnetic flux density is 1.60 T or more.
ここで、飽和磁束密度が１．６５Ｔ以上であることが好ましい。
また、鉄の原子パーセントａが、下記式 ８２≦ａ≦８６を満足することが好ましい。
また、ホウ素の原子パーセントｂが、下記式 ７≦ｂ≦９を満足することが好ましい。
また、合金元素として、更に炭素を含有し、合金組成がＦｅaＢbＳｉｃＰｄＣeで表わされ、炭素の原子パーセントｅは、下記式 ０＜ｅ＜ｄ、ｃ＋ｄ＋ｅ＜ｂ、ａ＋ｂ＋ｃ＋ｄ＋ｅ≦１００を満足することが好ましく、下記式 ０＜ｅ≦０．５を満足することがより好ましい。
また、保磁力が５Ａ／ｍ以下であり、有効透磁率が１００００（１ｋＨｚ，１Ａ／ｍ）以上であることが好ましい。
Here, the saturation magnetic flux density is preferably 1.65 T or more.
Moreover, it is preferable that the atomic percentage a of iron satisfies the following formula 82 ≦ a ≦ 86.
Moreover, it is preferable that the atomic percent b of boron satisfies the following formula 7 ≦ b ≦ 9.
Further, as an alloying element and further containing carbon, alloy composition represented by Fe a B b Si c P d C e, atomic percent e carbons, formula 0 <e <d, c + d + e <b, a + b + c + d + e It is preferable to satisfy ≦ 100, and it is more preferable to satisfy the following formula 0 <e ≦ 0.5.
Further, it is the coercive magnetic force 5A / m or less, it is preferred effective permeability is 10000 (1kHz, 1A / m) or more.
本発明の鉄基非晶質合金では、飽和磁束密度が１．６０Ｔ以上である必要があり、１．６５Ｔ以上であるのが好ましい。飽和磁束密度を１．６０Ｔ以上に限定するのは、目標とする軟磁性を達成するために必要だからである。
本発明の鉄基非晶質合金では、保磁力が５Ａ／ｍ以下であり、有効透磁率が１００００（１ｋＨｚ，１Ａ／ｍ）以上であるのが好ましい。
また、本発明の鉄基非晶質合金は、急冷凝固状態、及びアニール状態のいずれにおいても、密着曲げ変形が可能な靭性（ねばさ）を持つことが好ましく、また、断面積減少率が４０％以上の冷間加工性を持つことが好ましい。
また、本発明の鉄基非晶質合金は、急冷凝固状態よりアニール状態の方が硬さが、低下することが好ましい。
また、本発明の鉄基非晶質合金は、単ロール急冷凝固法により作製された厚さ０．０１〜０．０３ｍｍの帯状であることが好ましい。
また、本発明の鉄基非晶質合金は、キュリー温度と、キュリー温度より８０Ｋだけ高い温度との間の範囲内の温度では、結晶相が析出していないことが好ましい。
In the iron-based amorphous alloy of the present invention, the saturation magnetic flux density needs to be 1.60 T or more, and preferably 1.65 T or more. The saturation magnetic flux density is limited to 1.60 T or more because it is necessary to achieve the target soft magnetism.
The iron-based amorphous alloy of the present invention, the coercive magnetic force is not less less 5A / m, the effective permeability is 10000 (1kHz, 1A / m) is preferably at least.
Further, the iron-based amorphous alloy of the present invention preferably has toughness (stickiness) capable of tight bending deformation in both the rapidly solidified state and the annealed state, and the cross-sectional area reduction rate is 40. % Or more of cold workability is preferable.
The iron-based amorphous alloy of the present invention preferably has a lower hardness in the annealed state than in the rapidly solidified state.
Moreover, the iron-based amorphous alloy of the present invention is preferably in the form of a strip having a thickness of 0.01 to 0.03 mm produced by a single roll rapid solidification method.
In the iron-based amorphous alloy of the present invention, it is preferable that no crystal phase is precipitated at a temperature between the Curie temperature and a temperature higher by 80K than the Curie temperature.
急速凝固合金の評価方法
急速凝固リボン材の構造をＸ線回折法（理学電機(Bruker AXS)製、D8 Advance型）で調べることができる。ブロードなハローピークのみを示した試料において、示差走査熱量計（ＤＳＣ）を用いて、昇温速度０．６７Ｋ／ｓで、アルゴン雰囲気中で、磁気変態キュリー温度、結晶化開始温度、結晶化発熱量などを評価する。密度はトルエンを用いて、常温でアルキメデス法で測定した。硬さはビッカース硬度計を用いて、自由凝固面上で、負荷荷重100gで4回以上測定し、その平均値を採用する。なお、試料の熱処理は、リボン試料を減圧した石英管中に封入して、電気炉中で所定の温度と時間で行う。
磁気測定は、試料振動磁束計（ＶＳＭ）を用いて、８００ｋＡ／ｍの負荷磁場中で飽和磁束密度を常温で測定する。保磁力および最大透磁率をＢ−Ｈループトレーサーで、また、有効透磁率をインピーダンスアナライザーで１ｋＨｚ、１Ａ／ｍの条件下で、それぞれ、常温で測定する。さらに、磁気変態温度（キュリー温度）は、ＤＳＣ曲線から評価する。
Rapid evaluation of solidified alloy method structure X-ray diffraction method of rapid solidification ribbon material (Rigaku Electric (Bruker AXS) made, D8 Advance type) can be examined by. For samples showing only a broad halo peak, using a differential scanning calorimeter (DSC), the magnetic transformation Curie temperature, the crystallization start temperature, the crystallization exotherm in an argon atmosphere at a heating rate of 0.67 K / s. Evaluate the amount. The density was measured by the Archimedes method at room temperature using toluene. The hardness is measured 4 times or more with a load of 100 g on a free solidified surface using a Vickers hardness tester, and the average value is adopted. The heat treatment of the sample is performed at a predetermined temperature and time in an electric furnace by sealing the ribbon sample in a decompressed quartz tube.
In the magnetic measurement, the saturation magnetic flux density is measured at room temperature in a 800 kA / m load magnetic field using a sample vibration magnetometer (VSM). The coercive force and the maximum magnetic permeability are measured with a BH loop tracer, and the effective magnetic permeability is measured with an impedance analyzer at 1 kHz and 1 A / m at room temperature. Further, the magnetic transformation temperature (Curie temperature) is evaluated from the DSC curve.
以下に、本発明の鉄基非晶質合金を実施例に基づいて具体的に説明する。
上述のような母合金を用い、上述の急速凝固合金の作製方法によって作製され、かつ上述の急速凝固合金の評価方法によって評価された本発明の２６種の鉄基非晶質合金（実施例１〜２６）を表１に示す。
The iron-based amorphous alloy of the present invention will be specifically described below based on examples.
26 types of iron-based amorphous alloys of the present invention produced by the above-described method for producing a rapidly solidified alloy and evaluated by the above-described method for evaluating a rapidly solidified alloy (Examples) 1-2 6) shown in Table 1.
このようにして作製され、かつ評価された表１に示す本発明の実施例１〜２６の鉄基非晶質合金を用いて、本発明を説明する。
急速凝固層の同定
これらの実施例１〜２６の鉄基非晶質合金において、代表的な実施例６、９、２５及び２６の各合金組成の急速凝固リボン材のＸ線回折図形を図１〜図４に示す。図１〜図４から明らかなように、いずれの実施例のリボン合金もブロードな回折ピークのみを示しており、急速凝固リボン材は、結晶を含まないアモルファス相で構成されていることを示している。
なお、図示してはいないが、他の実施例１〜５、７〜８、及び１０〜２４のリボン合金もブロードな回折ピークのみを示しており、急速凝固リボン材は、結晶を含まないアモルファス相で構成されていることを示している。
The present invention will be described using the iron-based amorphous alloys of Examples 1 to 26 of the present invention shown in Table 1 that were prepared and evaluated in this manner.
Identification of Rapidly Solidified Layer In these iron-based amorphous alloys of Examples 1 to 26, X-ray diffraction patterns of rapidly solidified ribbon materials having typical alloy compositions of Examples 6 , 9, 25, and 26 are shown. 1 to 4 show. As is clear from FIGS. 1 to 4, the ribbon alloys of all the examples show only a broad diffraction peak, indicating that the rapidly solidified ribbon material is composed of an amorphous phase containing no crystals. Yes.
Although not shown, the ribbon alloys of other Examples 1 to 5, 7 to 8 and 10 to 24 also show only a broad diffraction peak, and the rapidly solidified ribbon material is an amorphous material containing no crystals. It is composed of phases.
図５〜図８は、Ｘ線回折でアモルファス相の生成を確認した代表的な実施例１、４、２５及び２６の各合金組成の急速凝固リボン試料のＤＳＣ曲線を示している。いずれの実施例の合金も、約２７０〜３６０度付近でキュリー温度に対応する小さな吸熱ピークを示した後、結晶化による明瞭な二つの発熱ピークを示しており、アモルファス相の結晶化が２段階で生じることを表している。なお、この２段階の結晶化挙動は、図示してはいないが、他の実施例２、３及び５〜２４のリボン合金でも、全て確認されている。また、第一発熱ピークと第二発熱ピークの温度間隔は鉄濃度の増加に伴って増大していることが認められる。いずれの合金においても、第一発熱ピークは、極めてシャープな形状となっており、第一発熱ピークに対応する析出物は、ナノサイズを持っておらず、しかもその析出が核発生・成長の様式で生じることを示唆している。なお、約７００〜７４０度付近の小さな吸熱反応ピークは、結晶析出物のキュリー温度に対応している。 5 to 8 show DSC curves of rapidly solidified ribbon samples of typical examples 1, 4, 25, and 26 having confirmed the formation of an amorphous phase by X-ray diffraction. Alloy either embodiment also, after showing a small endothermic peak corresponding to the Curie temperature at around 27 0-3 6 0 °, it shows a clear two exothermic peak due to crystallization, crystallization of the amorphous phase Is generated in two stages. The two-stage crystallization behavior is not shown in the figure, but all the ribbon alloys of Examples 2 , 3 and 5 to 24 have been confirmed. It can also be seen that the temperature interval between the first exothermic peak and the second exothermic peak increases with increasing iron concentration. In either alloy, the first exothermic peak is a very sharp shape, precipitates that corresponds to the first exothermic peak does not have a nano-sized, moreover deposition of nucleation and growth thereof Suggests that it occurs in a manner. Incidentally, a small endothermic reaction peak near about 7 0 0-7 4 0 degrees corresponds to the Curie temperature of the crystal precipitates.
図１０及び図１１に、それぞれ、実施例１８の急速凝固リボン材（熱処理材）をキュリー温度より２０度高い温度で真空減圧下で１０分間加熱後、水中に急速冷却した試料のＶＳＭ曲線、及びＢ−Ｈヒステリシス曲線を示している。図示してはいないが、他の実施例１〜１７、及び１９〜２６の急速凝固リボン合金材でも、急速冷却試料のＶＳＭ曲線、及びＢ−Ｈヒステリシス曲線が全て得られている。
図示の実施例１８の急速凝固リボン材の急速冷却試料のＶＳＭ曲線、及びＢ−Ｈヒステリシス曲線のいずれのデータも、これらの試料が典型的な軟磁気特性を有していることを示している。
本発明の鉄基非晶質合金のＢ−Ｈ曲線は、特に、図１１に示す実施例１８の熱処理材のヒステリシスＢ−Ｈ曲線のように、直線性に優れており、本発明の鉄基非晶質合金（実施例１８の熱処理材）を、例えば自動車用モータ磁心等に用いた場合、Ｂ−Ｈ曲線の比例的（直線的）に変化する関係がモータの制御に好ましいと言える。
FIGS. 10 and 11 respectively show a VSM curve of a sample rapidly heated in water after heating the rapidly solidified ribbon material (heat treated material) of Example 18 at a temperature 20 ° C. higher than the Curie temperature for 10 minutes under vacuum and reduced pressure. A BH hysteresis curve is shown. Although not shown, the VSM curve and the BH hysteresis curve of the rapidly cooled sample are all obtained in the other rapidly solidified ribbon alloy materials of Examples 1 to 17 and 19 to 26.
Both the VSM curve and BH hysteresis curve data of the rapidly cooled samples of the rapidly solidified ribbon material of Example 18 shown indicate that these samples have typical soft magnetic properties. .
The BH curve of the iron-based amorphous alloy of the present invention is excellent in linearity, particularly like the hysteresis BH curve of the heat-treated material of Example 18 shown in FIG. When the amorphous alloy (the heat-treated material of Example 18) is used for, for example, an automobile motor core, it can be said that a proportional (linear) change in the BH curve is preferable for motor control.
上述の表１は、これらのデータから算出した飽和磁束密度（Ｍｓ），保磁力(Ｈｃ)を、有効透磁率（μｅ）およびキュリー温度（Ｔｃ）と共にまとめたものである。
上述の表１から明らかなように、実施例１〜２６のすべての組成合金で、飽和磁束密度は１．６０Ｔ以上であり、一部の合金系では、１．７Ｔを上回り、１．７３Ｔに達していることが注目される。それらの合金の中で実施例１〜１０、１２、１３、及び１８の合金の保磁力は、５Ａ／ｍ以下であり、１kHzでの有効透磁率は１０４以上であり、最大有効透磁率は１０ ５ 以上となる大変優れた軟磁性を有している。なお、飽和磁束密度の鉄量依存性に注目する時、鉄濃度が約８４ａｔ％で飽和しており、それ以上に鉄濃度を増加しても、合金密度も上昇するために、結果としてほぼ飽和してしまうものと推定される。いずれにしても、これらの磁気特性はすべての合金で、本発明の目的を達成しているものであり、アモルファス金属、ガラス金属分野における新しい軟磁性アモルファス金属として、産業化が期待できるものである。
Table 1 above summarizes the saturation magnetic flux density (Ms) and coercivity (Hc) calculated from these data, together with the effective magnetic permeability (μe) and the Curie temperature (Tc).
As apparent from Table 1 above, the saturation magnetic flux density is 1.60 T or more in all the composition alloys of Examples 1 to 26, and in some alloy systems, it exceeds 1.7 T and reaches 1.73 T. It is noted that it has reached. The coercive force of alloys of Examples 1～10,12,13, and 18 among the alloys thereof, 5A / m Ri der less effective permeability at 1 kHz is over 10 4 or more, the maximum effective It has very good soft magnetism with a permeability of 10 5 or more . When focusing on the iron content dependency of the saturation magnetic flux density, the iron concentration is saturated at about 84 at%, and even if the iron concentration is further increased, the alloy density also rises. It is estimated that In any case, these magnetic properties have achieved the object of the present invention in all alloys, and can be expected to be industrialized as a new soft magnetic amorphous metal in the field of amorphous metal and glass metal. .
図１２及び図１３は、実施例１８のアモルファス合金（Ｆｅ８４Ｂ８．５Ｓｉ４．１０ Ｐ３。２５ Ｃ０．１５）の、それぞれ、急速凝固したままのリボン材および３２６℃で１０分加熱後水中に冷却したリボン材の１８０度密着曲げ変形後の引張り応力側の走査電子顕微鏡写真を示している。急速凝固材および熱処理材ともに、密着曲げ変形域には多数のせん断変形帯が発生しているが、破壊クラックは見られず、本軟磁性アモルファス合金が１８０度の密着曲げ延性を有しており、しかもその曲げ延性が最適熱処理後においても保持されている。これまで、極めて多数の鉄基のアモルファス合金およびガラス合金が作成、開発されてきたが、最適熱処理状態においても密着曲げ変形が可能であることを示したものは全くないものと思われている。このように、本発明の鉄基アモルファス合金群は、優れた軟磁気特性の外に、極めて優れた曲げ延性とその高い熱的安定性を保持している。 12 and 13, an amorphous alloy (Fe 84 B 8.5 Si 4. 10 P 3 .25 C 0. 1 5) of 10 respectively, with the ribbon material and 326 ° C. The as-rapidly solidified Example 18 The scanning electron micrograph by the side of the tensile stress after 180 degree | times adhesion bending deformation | transformation of the ribbon material cooled in water after minute heating is shown. Although both the rapidly solidified material and the heat-treated material have many shear deformation bands in the tight bending deformation region, no fracture cracks are observed, and this soft magnetic amorphous alloy has a tight bending ductility of 180 degrees. Moreover, the bending ductility is maintained even after the optimum heat treatment. To date, a large number of iron-based amorphous alloys and glass alloys have been created and developed, but it is believed that nothing has shown that adhesive bending deformation is possible even under optimum heat treatment conditions. Thus, the iron-based amorphous alloy group of the present invention retains extremely excellent bending ductility and its high thermal stability in addition to excellent soft magnetic properties.
Claims (12)
８１≦ａ≦８７、
７≦ｂ≦１０、
０＜ｄ≦ｃ＜ｃ＋ｄ＜ｂ、
ａ＋ｂ＋ｃ＋ｄ≦１００
を満足し、
飽和磁束密度が１．６０Ｔ以上であることを特徴とする高延性・高加工性を持つ高磁束密度軟磁性鉄基非晶質合金。 When the alloy element contains iron, boron, silicon and phosphorus, the alloy composition is represented by Fe a B b Si c P d , and a, b, c and d are atomic percent, a, b, c , And d are the following formulas 81 ≦ a ≦ 87,
7 ≦ b ≦ 10,
0 <d ≦ c <c + d <b,
a + b + c + d ≦ 100
Satisfied,
A high magnetic flux density soft magnetic iron-based amorphous alloy having high ductility and high workability, characterized by a saturation magnetic flux density of 1.60 T or more.
８２≦ａ≦８６
を満足する請求項１又は２に記載の鉄基非晶質合金。 Atomic percent a of the iron, the following formulas 82 ≦ a ≦ 86
The iron-based amorphous alloy according to claim 1 or 2, satisfying
７≦ｂ≦９
を満足する請求項１〜３のいずれか１項に記載の鉄基非晶質合金。 Atomic percent b of the boron, the following formula 7 ≦ b ≦ 9
The iron-based amorphous alloy according to any one of claims 1 to 3, which satisfies:
０＜ｅ＜ｄ、
ｃ＋ｄ＋ｅ＜ｂ
ａ＋ｂ＋ｃ＋ｄ＋ｅ≦１００
を満足する請求項１〜４のいずれか１項に記載の鉄基非晶質合金。 Wherein as an alloying element and further containing carbon, the alloy composition is represented by Fe a B b Si c P d C e, atomic percent e of the carbon, the following formula 0 <e <d,
c + d + e <b
a + b + c + d + e ≦ 100
The iron-based amorphous alloy according to any one of claims 1 to 4, wherein:
０＜ｅ≦０．５
を満足する請求項５に記載の鉄基非晶質合金。 Atomic percent e of the carbon, the following formula 0 <e ≦ 0.5
The iron-based amorphous alloy according to claim 5 satisfying
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