JPH0310052A - High permeability amorphous alloy having high corrosion resistance, high strength, and high wear resistance and improvement of magnetic property of same - Google Patents
High permeability amorphous alloy having high corrosion resistance, high strength, and high wear resistance and improvement of magnetic property of sameInfo
- Publication number
- JPH0310052A JPH0310052A JP2004575A JP457590A JPH0310052A JP H0310052 A JPH0310052 A JP H0310052A JP 2004575 A JP2004575 A JP 2004575A JP 457590 A JP457590 A JP 457590A JP H0310052 A JPH0310052 A JP H0310052A
- Authority
- JP
- Japan
- Prior art keywords
- amorphous alloy
- annealing
- atm
- corrosion resistance
- wear resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 32
- 230000035699 permeability Effects 0.000 title claims abstract description 31
- 230000007797 corrosion Effects 0.000 title claims abstract description 19
- 238000005260 corrosion Methods 0.000 title claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052711 selenium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052752 metalloid Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910052789 astatine Inorganic materials 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 20
- 239000000956 alloy Substances 0.000 abstract description 20
- 239000000203 mixture Substances 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 description 28
- 239000010959 steel Substances 0.000 description 28
- 230000000694 effects Effects 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000004907 flux Effects 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000005300 metallic glass Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017112 Fe—C Inorganic materials 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001004 magnetic alloy Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、高透磁率非晶質合金とその合金の磁気特性の
改善方法に関し、特に本発明は、高耐食性、高強度、高
耐摩耗性に優れると共に窒素を含有させることにより磁
気特性を改善した高透磁率非晶質合金について提案する
。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a high magnetic permeability amorphous alloy and a method for improving the magnetic properties of the alloy. We propose a high magnetic permeability amorphous alloy with excellent magnetic properties and improved magnetic properties by incorporating nitrogen.
本発明の如き窒素含前非晶質合金としては、例えば、特
開昭５４−９４４２８号では、Ｃｒ、 Ｆｅ、 Ｃｏお
よびＮｉからなる群から選択された少なくとも１つの遷
移金属と、Ｂ、 Ｓｉ、 ＡＩ、 ＣおよびＰからなる
群から選択された少なくとも１つの元素と、窒素との合
金で構成され、その窒素含有量がｌ ａｔａ＋％（以下
は単に「％」で表示する。）よりも大であるアモルファ
ス金属膜を提案している。The nitrogen-containing amorphous alloy according to the present invention, for example, in JP-A-54-94428, contains at least one transition metal selected from the group consisting of Cr, Fe, Co and Ni, B, Si, It is composed of an alloy of at least one element selected from the group consisting of AI, C, and P and nitrogen, and the nitrogen content is greater than l ata+% (hereinafter simply expressed as "%"). We are proposing an amorphous metal film.
また、特開昭６０−１５２６５１号には、ＭＸ Ｌ、Ｎ
２（ただし、Ｎ：金属、Ｌ ： Ｂ、 Ｓｔなどの半金
属または半導体元素、ｘ＋ｙ＋ｚ＝１００ 、ｙ＋ｚ≧
１０、Ｘ≠０、ｙ≠０．２≠０）からなる窒素を含む非
晶質合金を提案している。In addition, MX L, N
2 (however, N: metal, L: semimetal or semiconductor element such as B, St, x+y+z=100, y+z≧
10, X≠0, y≠0.2≠0).
さらにまた特公昭５９−１８４６１号では、合金原料を
窒素雰囲気中で溶融して所望の形状に急冷凝固させるこ
とにより耐食性１８０°密着曲げに優れる急冷凝固金属
材料の製造方法を提案しており、特公昭６０−１３７３
号あるいは特公昭６０−１３７５号では、非晶質合金の
母合金中に窒素を含有させた原料を溶融状態から所定の
冷却速度で急冷凝固させることを特徴とする強度および
耐食性のすぐれた非晶質合金の製造方法を提案しており
、特公昭５８−１１８３号では、原子比率でＳｉ３〜１
６％、８５〜２４％で、しかもＳｔとＢとの和１８〜２
７％、 Ｎｉ Ｏ，１〜４０％。Furthermore, Japanese Patent Publication No. 59-18461 proposes a method for producing a rapidly solidified metal material with excellent corrosion resistance and 180° tight bending by melting alloy raw materials in a nitrogen atmosphere and rapidly solidifying them into a desired shape. Kosho 60-1373
No. 60-1375 discloses an amorphous alloy with excellent strength and corrosion resistance, which is characterized by rapidly solidifying a raw material in which nitrogen is contained in a mother alloy of an amorphous alloy from a molten state at a predetermined cooling rate. In Japanese Patent Publication No. 1183/1983, the atomic ratio of Si3 to 1 is proposed.
6%, 85-24%, and the sum of St and B is 18-2
7%, NiO, 1-40%.
残部Ｆｅよりなる磁束密度が高く角形比の大きい高１Ｆ
ｉｔｉ率非晶質合金を提案し、そして特開昭６０−１２
８２３５号によれば、原子比率でＮｉ７６〜８１％、Ｃ
ｒ２〜６％、 Ｓｔ Ｏ，０５〜１．５％、 ＯＯ，０
１％以下、ＮＯ，００５％以下、残部Ｆｅおよび不可避
的不純物からなる高透磁率磁性合金が開示されており、
そこではＮはＯと同様に透磁率を低下させる元素であり
、含有量を０．００５％以下に抑える必要があることが
示されている。High 1F with high magnetic flux density and high squareness ratio, with the remainder being Fe.
proposed an amorphous alloy with an itis ratio, and published JP-A-60-12
According to No. 8235, the atomic ratio is 76 to 81% Ni, C
r2~6%, St O, 05~1.5%, OO, 0
A high permeability magnetic alloy consisting of 1% or less NO, 0.005% or less, the balance Fe and unavoidable impurities is disclosed,
It is shown that N, like O, is an element that lowers magnetic permeability, and that it is necessary to suppress the content to 0.005% or less.
前記特開昭５４−９４４２８号に記載された発明のアモ
ルファス金属膜の窒素含有量はｌ原子％より大であり、
これにより磁化（４ｘＭｓ）の下降、固有抵抗の増大を
図った非晶質金属膜である。なお、１原子％より大きな
窒素含有量となすためには、同公報特許請求の範囲第２
項に記載されているように、プラズマ中に少なくとも２
体積％のＮ２ガスを含む室内でスパッタリング法により
製造されることが前提となることが明らかであり、溶融
状態から高速移動冷却面上に噴射され、急冷・凝固され
てなるいわゆる急冷°・凝固非晶質金属帯ではない。そ
のため、同公報記載発明の金属膜では、高強度ならびに
耐摩耗性は期待できない。さらにまたこの金属膜は硬質
磁性膜であって高磁束密度、高電気抵抗ならびに高角型
比を有する金属膜であって、軟磁性材料ではないので、
高透磁率を目的とする材料ではない。The nitrogen content of the amorphous metal film of the invention described in JP-A-54-94428 is greater than 1 atomic %,
As a result, the amorphous metal film is designed to lower magnetization (4xMs) and increase specific resistance. In addition, in order to make the nitrogen content larger than 1 atomic %, it is necessary to refer to Claim 2 of the same publication.
At least 2
It is clear that the premise is that the product is manufactured by sputtering in a room containing vol.% N2 gas, and is injected from a molten state onto a fast-moving cooling surface and rapidly cooled and solidified. It is not a crystalline metal band. Therefore, high strength and wear resistance cannot be expected from the metal film of the invention described in the publication. Furthermore, this metal film is a hard magnetic film with high magnetic flux density, high electrical resistance, and high squareness ratio, and is not a soft magnetic material.
This material is not intended for high magnetic permeability.
前記特開昭６０−１５２６５１号記載の発明の窒素を含
む非晶質合金は、前記特開昭５４−９４４２８号記載の
発明を改良した非晶質合金であり、同公報には窒素含有
量は５原子％以上が望ましいと記載されている。しかし
、このように多量の窒素を含有させるのは硬質磁性を向
上させることを目的とし、かつスパッタリング法により
製造される非晶質合金であるが、それ故に高強度ならび
に耐摩耗性は期待できず、また前述したように高磁束密
度、高電気抵抗ならびに高角型比を有する硬質磁性非晶
質合金を提供することを達成しているが、軟磁性材料で
はないため高透磁率を有する金属材料は得られない。The nitrogen-containing amorphous alloy of the invention described in JP-A-60-152651 is an improved amorphous alloy of the invention described in JP-A-54-94428, and the publication states that the nitrogen content is It is stated that 5 atomic % or more is desirable. However, the purpose of containing such a large amount of nitrogen is to improve hard magnetism, and the amorphous alloy is manufactured by a sputtering method, so high strength and wear resistance cannot be expected. Also, as mentioned above, it has been achieved to provide a hard magnetic amorphous alloy with high magnetic flux density, high electrical resistance, and high squareness ratio, but since it is not a soft magnetic material, a metallic material with high magnetic permeability is I can't get it.
次に前記特公昭５９−１８４６１号記載の発明によれば
、製造されるＦｅ−Ｐ−Ｃ−Ｃｒ系急冷凝固金属材料の
特性として耐食性、 １８０＠密着曲げ等を改善する
ことを目的とし、窒素雰囲気中で溶融して、所定量の窒
素を含有させることにより、前記特性を改善することを
提案している。しかし、そこには、該発明により製造さ
れる材料の電磁気特性については何らの教示あるいは示
唆もなされていない。Next, according to the invention described in Japanese Patent Publication No. 59-18461, nitrogen is It has been proposed to improve these properties by melting in an atmosphere and incorporating a predetermined amount of nitrogen. However, there is no teaching or suggestion regarding the electromagnetic properties of the materials produced according to the invention.
また、前記特公昭６０−１３７３号および特公昭６０１
３７５号記載の発明によれば、基本成分としてＦｅ。In addition, the above-mentioned Special Publication No. 60-1373 and Special Publication No. 601
According to the invention described in No. 375, Fe is used as a basic component.
ＣＯおよびＮｉの１種または２種以上と、ＮおよびＡＩ
の１種または２種以上とさらに半金属元素としてＢ、Ｃ
，ＰおよびＳｉの２種以上に、ＴｉおよびＺｒの１種ま
たは２種を含有する原料を、溶融状態から所定温度まで
の温度範囲内で所定冷却速度で急冷凝固させて強度およ
び耐食性のすぐれた非晶質合金を製造することができる
と記載されているが、このように製造された合金につい
ての電磁気特性については何らの教示あるいは示唆もな
されていない。One or more types of CO and Ni, and N and AI
One or more of the following and further B, C as metalloid elements
, P and Si and one or two of Ti and Zr are rapidly solidified at a predetermined cooling rate within a temperature range from a molten state to a predetermined temperature to produce a material with excellent strength and corrosion resistance. Although it is stated that amorphous alloys can be produced, there is no teaching or suggestion as to the electromagnetic properties of the alloys so produced.
本発明者らは、上述したような特性を有する急冷凝固金
属材料は、前記既知の特性以外にも成る種の工夫を加え
れば簡単に高透磁率特性を有する材料になることを知見
して、高耐食性、高強度。The present inventors have found that a rapidly solidified metal material having the above-mentioned characteristics can easily be made into a material having high magnetic permeability by adding some kind of device other than the known characteristics, High corrosion resistance, high strength.
高耐摩耗性を具えるとともに、高透磁率に優れる本発明
の非晶質合金に想到したのである。The inventors have come up with the amorphous alloy of the present invention, which has high wear resistance and excellent magnetic permeability.
すなわち本発明は、高透磁率非晶質合金と、その合金の
磁気特性を改善する方法を提供することを目的とし、さ
らに他の目的は、高透磁率と共に高耐食性、高強度、高
耐摩耗性にも優れる非晶質合金とその合金の磁気特性の
改善方法を提供することを目的とするものであり、特許
請求の範囲記載の合金とその合金の磁気特性の改善方法
を提供することによって前記目的を達成することができ
る。なお、本発明の非晶質合金は、同合金中に少なくと
も５０％の非晶質組織を有する合金を意味するものとす
る。That is, an object of the present invention is to provide a high magnetic permeability amorphous alloy and a method for improving the magnetic properties of the alloy. The object of the present invention is to provide an amorphous alloy that has excellent properties and a method for improving the magnetic properties of the alloy, and by providing the alloy described in the claims and a method for improving the magnetic properties of the alloy. The above objective can be achieved. Note that the amorphous alloy of the present invention means an alloy having at least 50% amorphous structure in the alloy.
すなわち、本発明は、
原子比率で下記の式
％式％
（但し、Ｍは、Ｆｅ、 Ｃｏ、 Ｎｉのなかから選ばれ
るいずれか少なくとも１種の遷移金属元素；Ｙは、Ｓｉ
、 Ｂ、 Ｐ、 Ｇｅ、 Ｓｅのなかから選ばれるい
ずれか少なくとも１種の半金属元素：Ｚは、Ｗ、 Ｎｏ
、 Ｖ、 Ｎｂ、 Ｔａ、 Ｔｉ、 Ｈｆ、 Ｍｎ、
Ｃｕのなかから選ばれるいずれか少なくとも１種の金
属元素；
Ｎは窒素であり、ａ、 ｂ、 ｃおよびｆは、それぞれ
５５．０５ ａ≦９０．０％、 １０．０≦ｂ≦４０．
０％、 ０．０１≦ｃ≦３０．０％、 ０．００２≦ｒ
≦０．３％である。）よりなる高耐食性、高強度、高耐
摩耗性に優れる高透磁率非晶質合金である。That is, the present invention has the following formula in atomic ratio: % (where M is at least one transition metal element selected from Fe, Co, and Ni; Y is Si
, B, P, Ge, Se: Z is W, No.
, V, Nb, Ta, Ti, Hf, Mn,
at least one metal element selected from Cu; N is nitrogen; a, b, c and f are each 55.05, a≦90.0%, 10.0≦b≦40.
0%, 0.01≦c≦30.0%, 0.002≦r
≦0.3%. ) is a high magnetic permeability amorphous alloy with excellent corrosion resistance, high strength, and high wear resistance.
また本発明は、高耐食性、高強度、高耐摩耗性に優れる
上記高透磁率非晶質合金を、非酸化性雰囲気中で結晶化
温度範囲内で焼鈍することにより、磁気特性を改善する
方法を提供するものである。The present invention also provides a method for improving magnetic properties by annealing the above-mentioned high magnetic permeability amorphous alloy, which is excellent in high corrosion resistance, high strength, and high wear resistance, within the crystallization temperature range in a non-oxidizing atmosphere. It provides:
本発明者らは、前記特公昭５Ｂ−１１８３号記載の高透
磁率非晶質合金の磁気特性をさらに改善することを目的
として研究を開始した。ところで、上述したように、従
来電磁気特性に優れる結晶質合金にあっては、Ｎの含有
が前記特性に悪影響を及ぼすことが、例えば前記特開昭
６０−１２８２３５号により知られていることから、非
晶質合金を溶製する際の雰囲気中のＮ含有量が磁気特性
に定量的にどのように影響するかの予備試験を行った。The present inventors began research with the aim of further improving the magnetic properties of the high magnetic permeability amorphous alloy described in Japanese Patent Publication No. 5B-1183. By the way, as mentioned above, it is known from, for example, the above-mentioned Japanese Patent Laid-Open No. 60-128235, that in crystalline alloys that conventionally have excellent electromagnetic properties, the inclusion of N has an adverse effect on the properties. A preliminary test was conducted to determine how the N content in the atmosphere when melting an amorphous alloy quantitatively affects magnetic properties.
ところが、従来磁気特性に悪影響を及ぼすことの知られ
たＮの含有量の増加が磁気特性、なかでも透磁率に対し
ては、逆に悪影響を及ぼきず、むしろＮの所定の含有量
範囲内においては、含有量が高いほど顕著な効果を示す
ことを新規に知見し、本発明を完成した。However, an increase in the content of N, which is conventionally known to have a negative effect on magnetic properties, does not have a negative effect on magnetic properties, especially magnetic permeability; on the contrary, within a predetermined N content range, has newly discovered that the higher the content, the more pronounced the effect, and completed the present invention.
さらに本発明者らは、Ｚ元素群すなわち、Ｗ。Furthermore, the inventors discovered that the Z element group, namely W.
Ｍｏ、 Ｖ、 Ｎｂ、 Ｔａ、 Ｔｉ、 Ｈｆ、 Ｍｎ
、 Ｃｕなどの元素は、耐食性１強度、耐摩耗性の向上
に寄与する元素であることは知られていることから、磁
気特性に対してどのような影響を及ぼすかについて試験
した。Mo, V, Nb, Ta, Ti, Hf, Mn
Since it is known that elements such as Cu, etc. contribute to improvements in corrosion resistance, strength, and wear resistance, tests were conducted to determine how they affect magnetic properties.
その結果、前記Ｚ元素群中の１部の元素を添加含有させ
た非晶質合金は、磁気特性に対して悪影響を及ぼすこと
がわかった。そこで、上述したＮに対する知見にもとづ
き、前記Ｚ元素群の含有による耐食性９強度、耐摩耗性
の向上を維持しながら、さらにそれらの添加に伴う磁気
特性の低下を抑制する手段としてＮに着目し、このＮを
含有させることの効果について研究を行った。その結果
、Ｚ元素群およびＮの複合添加は、前記本発明合金の目
的とするすべての特性を満足させることができることを
知見した。As a result, it was found that an amorphous alloy containing a part of the element in the Z element group has an adverse effect on magnetic properties. Therefore, based on the above-mentioned knowledge regarding N, we focused on N as a means to maintain the improvements in corrosion resistance9 strength and wear resistance due to the addition of the Z element group, while further suppressing the deterioration of magnetic properties caused by the addition of these elements. , conducted research on the effect of containing this N. As a result, it was found that the combined addition of the Z element group and N can satisfy all the desired properties of the alloy of the present invention.
次に、本発明において成分組成を限定する理由を説明す
る。Next, the reason for limiting the component composition in the present invention will be explained.
Ｆｅ、 Ｃｏ、 Ｎｉのなかから選ばれるいずれか少な
くとも１種の遷移元素であるＭが５５．０％より少ない
と、十分な強度、耐摩耗性ならびに透磁率が得られず、
一方、９０．０％より多いと溶融状態から急冷・凝固さ
せても非晶質合金が得られないので、Ｍは５５．０〜９
０．０％の範囲内にする必要がある。If M, which is at least one transition element selected from Fe, Co, and Ni, is less than 55.0%, sufficient strength, wear resistance, and magnetic permeability cannot be obtained.
On the other hand, if it exceeds 90.0%, an amorphous alloy cannot be obtained even if it is rapidly cooled and solidified from the molten state, so M is 55.0 to 9.
It is necessary to keep it within the range of 0.0%.
Ｓｉ、 Ｂ、 Ｐ、 Ｇｅ、 Ｓｅのなかから選ばれ
るいずれか少なくとも１種の半金属元素Ｙが１０．０％
より少ないと、溶融状態から急冷・凝固させても非晶質
合金が得られず、一方、４０．０％より多いと十分な耐
食性９強度、耐摩耗性ならびに透磁率が得られないので
、Ｙは１０．０〜４０．０％の範囲内にする必要がある
。10.0% of at least one metalloid element Y selected from Si, B, P, Ge, and Se
If it is less than 40.0%, an amorphous alloy cannot be obtained even if it is rapidly cooled and solidified from the molten state.On the other hand, if it is more than 40.0%, sufficient corrosion resistance 9 strength, wear resistance and magnetic permeability cannot be obtained. must be within the range of 10.0 to 40.0%.
なお、Ｙ元素を２種以上含有させると、非晶質化がさら
に容易になるので好ましい。Note that it is preferable to contain two or more types of Y elements, since this makes amorphization easier.
Ｗ、 Ｎｏ、 Ｖ、 Ｎｂ、 Ｔａ、 Ｔｉ、 Ｈｆ
、 Ｍｎ、 Ｃｕの中から選ばれるいずれか少なくとも
１種の周期律表ＩＶａ。W, No, V, Nb, Ta, Ti, Hf
, Mn, and Cu in the periodic table IVa.
Ｖａ、 Ｖｌａ、■ａ、Ｉｂ族の金属元素Ｚが０．０１
％より少ないと十分な耐食性２強度ならびに耐摩耗性が
得られず、一方、３０．０％より多いと十分な透磁率が
得られないので、Ｚはｏ、ｏｉ〜３０．０％の範囲内に
する必要がある。Va, Vla, ■ a, Ib group metal element Z is 0.01
If it is less than 30.0%, sufficient corrosion resistance 2 strength and wear resistance cannot be obtained, while if it is more than 30.0%, sufficient magnetic permeability cannot be obtained, so Z is within the range of o, oi to 30.0%. It is necessary to
窒素は、透磁率の向上に寄与することを本発明者らが初
めて知見した元素であり、Ｎが０．００２％より少ない
と十分な透磁率が得られず、一方、０．３％より多く合
金中にＮを含有させることは実質的に困難であるので、
Ｎは０．００２〜０．３％の範囲内にする必要がある。Nitrogen is an element that the present inventors discovered for the first time to contribute to improving magnetic permeability, and if N is less than 0.002%, sufficient magnetic permeability cannot be obtained, whereas if it is more than 0.3% Since it is substantially difficult to incorporate N into the alloy,
N needs to be within the range of 0.002 to 0.3%.
実施例１
第１表は、Ｆｅ−Ｎｉ−５ｔ −Ｂ −Ｎ系とＦｅ−Ｃ
ｏ−３ｉＢ−Ｎ系にさらにＷを加えた成分組成を有する
アモルファス合金リボンを作製したものである。Example 1 Table 1 shows Fe-Ni-5t-B-N system and Fe-C
An amorphous alloy ribbon having a composition in which W was further added to the o-3iB-N system was produced.
このアモルファスリボンは、第１表に示すそれぞれの母
合金を、石英ガラス管内で加熱・溶融し、前記管の先端
に設けられた０、３ｗｍ Ｘ ５ ｍｌのスリット状ノ
ズルから銅製単ロールの回転表面上に噴出・急冷・凝固
させることにより作製した。その際のロールの周速は２
７ｍ／ｓｅｃであり、噴出させるときの石英ガラス管内
のガス圧は＋０．４ ｋｇ／ｃｍｉ”であり、噴出・急
冷・凝固させたときの雰囲気はＮまたはＡｒを用いた。This amorphous ribbon is produced by heating and melting each of the master alloys shown in Table 1 in a quartz glass tube, and applying it to the rotating surface of a single copper roll through a 0.3 wm x 5 ml slit-shaped nozzle provided at the tip of the tube. It was made by jetting, quenching, and solidifying. The circumferential speed of the roll at that time is 2
7 m/sec, the gas pressure inside the quartz glass tube at the time of ejection was +0.4 kg/cmi'', and the atmosphere during ejection, rapid cooling, and solidification was N or Ar.
また、その際の冷却速度は約１０’℃／ｓｅｅであり、
得られたリボンの寸法は幅約４．５■ｌ、厚さ３５μ−
であった。In addition, the cooling rate at that time is approximately 10'°C/see,
The dimensions of the obtained ribbon were approximately 4.5 μl in width and 35 μm in thickness.
Met.
次に、これらの製造したアモルファス合金リボンを、作
製したまま無処理（ａｓ ｃａｓｔ）のもの、および４
５０℃でｌｈｒ非酸化性雰囲気中で焼鈍したものについ
て最大透磁率μ、および初期透磁率μ。Next, these produced amorphous alloy ribbons were as-cast, as-cast, and as-cast.
Maximum permeability μ, and initial permeability μ for annealed at 50° C. in lhr non-oxidizing atmosphere.
を測定した。was measured.
また、前記ａｓ ｃａｓｔのリボンについて、引張強さ
（ｋｇ７ａｍす、硬度（Ｈｖ）およびｌＮ−ＨＣｌ水溶
液に３５℃で１００ ｈｒ浸漬したときの腐食量（μｍ
／１００ ｈｒ）を測定した。In addition, regarding the as cast ribbon, the tensile strength (kg7am), hardness (Hv), and corrosion amount (μm) when immersed in an IN-HCl aqueous solution for 100 hours at 35°C
/100 hr) was measured.
これらの結果を第１表に示す。なお、結晶化温度（℃゛
）およびキュリー点（’Ｃ）も同表に示す。These results are shown in Table 1. The crystallization temperature (°C) and Curie point ('C) are also shown in the same table.
なお、前記透磁率はソレノイドコイル中において測定し
た。Note that the magnetic permeability was measured in a solenoid coil.
この第１表かられかるように、患１〜４発明鋼にあって
は、ａｓ ｃａｓｔＯものよりも、４５０℃×１ｈｒ焼
鈍したものの方が、μ、は１．５〜３．０倍と増加して
おり、μ。も１．３〜２倍と増加している。As can be seen from Table 1, for the Inventive Steels 1 to 4, the value of μ increased by 1.5 to 3.0 times in the steels annealed at 450°C for 1 hour than in the as castO steels. and μ. It has also increased by 1.3 to 2 times.
次にＮｉ ４，４％、Ｗ ０．５％を含有し、Ｎを０．
００５５％含有する嵐１発明鋼と、Ｎｉ ４．４％、
Ｗ ０．５％。Next, it contains 4.4% Ni, 0.5% W, and 0.5% N.
Arashi 1 invention steel containing 0.0055%, Ni 4.4%,
W 0.5%.
Ｎ Ｏ，００１７％含有する！１１１Ｌ５比較鋼にあっ
ては、μ。Contains 17% NO! 111L5 comparative steel, μ.
は前者のａｓ ｃａｓｔのもの、焼鈍したものの方が後
者のものよりそれぞれ約２倍と高く、μ。はほぼ同一で
ある。The former as cast and annealed ones are about twice as high as the latter, respectively, and μ. are almost the same.
Ｎｉ ２４，７％、 Ｗ ０．４４％、Ｎを０ 、００
３４％含有する１ｌｈ２発明鋼と、Ｎｉ、 Ｗは同一含
有量でＮのみが０．００１７％と低い隘６比較鋼のμ、
は前者ａｓ ｃａｓｔのものでば約２倍、焼鈍したもの
では３〜４倍と高くなっており、μ。は前者のａｓ ｃ
ａｓｔおよび焼鈍したものの方が後者比較鋼よりそれぞ
れ約２倍になっていることがわかる。Ni 24.7%, W 0.44%, N 0.00
The μ of the 1lh2 invention steel containing 34% and the comparison steel with the same Ni and W content but only N being low at 0.0017%.
is about twice as high for the former as cast one, and three to four times higher for the annealed one, and μ. is the former as c
It can be seen that the ast and annealed steels each have about twice the strength of the latter comparison steel.
なお、Ｎｉ０代わりにＣＯを含有させた患３，４発明鋼
および患７．８比較鋼についてのμ。、μ。In addition, μ for the invention steels 3 and 4 and the comparison steel 7.8 containing CO instead of Ni0. , μ.
の挙動は上記Ｎｉを含有する発明鋼、比較鋼とほぼ同一
の傾向がみられる。The behavior is almost the same as that of the above-mentioned Ni-containing invention steel and comparative steel.
１Ｉｋ１１〜４発明鋼と、胤５〜８比較鋼とは、ともに
Ｗを含有することにより引張強さ（ｋｇ／ｍｍ”）、
Ｉｌｖ。1Ik11-4 invention steel and Seed 5-8 comparison steel both have a tensile strength (kg/mm") due to containing W,
Ilv.
腐食量はそれぞれ大差はなく、高強度、高耐摩耗性 高
耐食性を有しているが、一方、Ｗの含有により比較鋼に
みられる低いμ７が、本発明鋼にあってはＮの含有量を
多くすることによって、上記緒特性が維持されながら極
めて顕著な磁気特性の改善された非晶質合金である点に
おいて、本発明は刑目すべき発明である。There is no significant difference in the amount of corrosion, and the steels have high strength, high wear resistance, and high corrosion resistance. The present invention is a remarkable invention in that it is an amorphous alloy whose magnetic properties are significantly improved while maintaining the above-mentioned characteristics by increasing the amount of .
実施例２
第２表はＦｅ −（Ｎｉ、 Ｃｏ） −５ｉ−Ｂ−Ｎ系
合金に対し、さらにＰ、 Ｍｏ、 Ｖ、 Ｎｂ、 Ｔａ
、 Ｔｉ、 Ｍｎ、 Ｃｕ。Example 2 Table 2 shows the Fe-(Ni, Co)-5i-B-N alloy, and further contains P, Mo, V, Nb, and Ta.
, Ti, Mn, Cu.
Ｈｆ、 ＧｅおよびＳｅのいずれか少なくとも１種を加
えた成分組成を有するアモルファス合金リボンを、実施
例１と同一条件で作製した。第２表に発明鋼（隘２１〜
２８）と比較鋼（隠２９〜２１６）について透磁率、硬
度や引張強さなどの機械的性質、耐食性、結晶化温度、
キュリー点を測定した結果を示す。An amorphous alloy ribbon having a composition containing at least one of Hf, Ge, and Se was produced under the same conditions as in Example 1. Table 2 shows the invention steel (21~
28) and comparative steels (Hidden 29-216), mechanical properties such as magnetic permeability, hardness and tensile strength, corrosion resistance, crystallization temperature,
The results of measuring the Curie point are shown.
この第２表から判るように、Ｎｉ ２０．５％、 Ｓｉ
９．８％、 ８１４．１％、 Ｎｏ １．０％、
Ｖ ０．５％、 Ｎを０ 、００７％含有する嵐２１発
明鋼と、Ｎ Ｏ，００１３％含有する尚２９比較鋼とを
比較すると、μ醜、μ。は前者のａｓｃａｓｔ材および
焼鈍材とも本発明鋼の方が後者（比較鋼）よりも、μ■
μ。ともにそれぞれ約１．６倍と高い。また、基本組成
の他に添加元素としてＰ、 Ｎｂ、 Ｔａ、 Ｔｉ、
Ｍｎ、 Ｃｕ、 Ｉｆｆ、 ＧｅおよびＳｅのいずれか
１種を含有する魚２２〜２８発明鋼についてのμ■。As can be seen from this Table 2, Ni 20.5%, Si
9.8%, 814.1%, No 1.0%,
Comparing the Arashi 21 invention steel containing 0.5% V and 0.007% N with the Comparative Steel 29 containing 13% NO, the results are ugly and μ. The inventive steel has a higher μ■
μ. Both are about 1.6 times higher. In addition to the basic composition, additional elements such as P, Nb, Ta, Ti,
μ■ for Fish 22-28 invention steels containing any one of Mn, Cu, Iff, Ge and Se.
μ。の挙動は、上記のＭＯ，Ｖを含有する発明鋼（７に
２１）とほぼ同一の傾向がみられることが判った。μ. It was found that almost the same tendency was seen in the behavior of the above-mentioned invention steels containing MO and V (7 to 21).
実施例３
第１表に示す隘２発明鋼のリボンを作製し、４０００ｅ
の磁場中で４５０°Ｃまで加熱して２時間焼鈍した後、
前記磁場中で冷却した。その結果、第１表のＮ［Ｌ２発
明鋼のμ、およびμ。は、それぞれμ、 ： ３６０
，０００ 、μ。： ３３，０００の磁気特性となり、
第１表階２発明鋼のａｓ ｃａｓｔの磁気特性と比較し
て約２〜４倍改善された。Example 3 A ribbon of the invention steel shown in Table 1 was prepared and 4000e
After heating to 450°C in a magnetic field and annealing for 2 hours,
Cooled in the magnetic field. As a result, N[μ of L2 invention steel, and μ in Table 1. are μ, respectively: 360
,000,μ. : The magnetic properties are 33,000,
The magnetic properties were improved by about 2 to 4 times compared to the as cast magnetic properties of the second invention steel in Table 1.
実施例４
第１表に示す寛２発明鋼のアモルファスリボンについて
、１０ｋｇ／、１１２の張力を加えながら、４５０℃で
約１時間焼鈍した結果、μ、 ：ａｏｏ、ｏｏｏ、μ
。： ２９，０００の磁気特性が得られ、第１表１Ｉｋ
ｌＬ２発明鋼のａｓ ｃａｓｔの場合の磁気特性と比較
して約３倍改善された。Example 4 The amorphous ribbon of Kan 2 invention steel shown in Table 1 was annealed at 450°C for about 1 hour while applying a tension of 10 kg/, 112, and the results were as follows: μ, :aoo, ooo, μ
. : 29,000 magnetic properties were obtained, Table 1 1Ik
The magnetic properties of the IL2 invention steel were improved by about 3 times compared to the as cast case.
以上説明したように本発明によれば、従来の高透磁率非
晶質合金に比べさらに磁気特性に優れた高透磁率非晶質
合金を得ることができる。また、本発明によれば、Ｎ元
素の添加により、強度、硬度が向上し、機械的性質をも
向上させることができる。すなわち、従来高透磁率合金
が使われている変圧器、モーターなどの鉄心、磁気ヘッ
ドのコア材として最適な強度、耐食性、耐摩耗性に優れ
た高透磁率非晶質合金を提供することができる。As explained above, according to the present invention, it is possible to obtain a high magnetic permeability amorphous alloy that has more excellent magnetic properties than conventional high magnetic permeability amorphous alloys. Further, according to the present invention, by adding the N element, strength and hardness can be improved, and mechanical properties can also be improved. In other words, it is possible to provide a high magnetic permeability amorphous alloy with excellent strength, corrosion resistance, and wear resistance that is ideal for the core materials of transformers, motors, etc., and magnetic head core materials, where high magnetic permeability alloys have traditionally been used. can.
Claims (1)
ずれか少なくとも１種の遷移金属元素； Ｙは、Ｓｉ、Ｂ、Ｐ、Ｇｅ、Ｓｅのなかから選ばれるい
ずれか少なくとも１種の半金属元素； Ｚは、Ｗ、Ｍｏ、Ｖ、Ｎｂ、Ｔａ、Ｔｉ、Ｈｆ、Ｍｎ、
Ｃｕのなかから選ばれるいずれか少なくとも１種の金属
元素； Ｎは窒素であり、 ａ、ｂ、ｃおよびｆは、それぞれ ５５．０≦ａ≦９０．０ａｔｍ％、１０．０≦ｂ≦４０
．０ａｔｍ％、０．０１≦ｃ≦３０．０ａｔｍ％、０．
００２≦ｆ≦０．３ａｔｍ％である。） よりなる高耐食性、高強度、高耐摩耗性に優れる高透磁
率非晶質合金。 ２、原子比率で下記の式 ＭａＹｂＺｃＮｆ （但し、Ｍは、Ｆｅ、Ｃｏ、Ｎｉのなかから選ばれるい
ずれか少なくとも１種の遷移金属元素； Ｙは、Ｓｉ、Ｂ、Ｐ、Ｇｅ、Ｓｅのなかから選ばれるい
ずれか少なくとも１種の半金属元素； Ｚは、Ｗ、Ｍｏ、Ｖ、Ｎｂ、Ｔａ、Ｔｉ、Ｈｆ、Ｍｎ、
Ｃｕのなかから選ばれるいずれか少なくとも１種の金属
元素； Ｎは窒素であり、 ａ、ｂ、ｃおよびｆは、それぞれ ５５．０≦ａ≦９０．０ａｔｍ％、１０．０≦ｂ≦４０
．０ａｔｍ％、０．０１≦ｃ≦３０．０ａｔｍ％、０．
００２≦ｆ≦０．３ａｔｍ％である。） よりなる高耐食性、高強度、高耐摩耗性に優れる高透磁
率非晶質合金を、非酸化性雰囲気中で結晶化温度以下の
温度で焼鈍することを特徴とする磁気特性の改善方法。 ３、焼鈍を、磁場および／または張力を付加した状態の
もとで行うことを特徴とする特許請求の範囲第２項記載
の改善方法。 ４、焼鈍に当っては、焼鈍後の冷却を２００℃／ｓｅｃ
以下の速度で冷却することを特徴とする特許請求の範囲
第２項または３項に記載の改善方法。[Claims] 1. The following formula MaYbZcNf in atomic ratio (where M is at least one transition metal element selected from Fe, Co, and Ni; Y is Si, B, P, At least one metalloid element selected from Ge and Se; Z is W, Mo, V, Nb, Ta, Ti, Hf, Mn,
At least one metal element selected from Cu; N is nitrogen; a, b, c and f are respectively 55.0≦a≦90.0 atm%, 10.0≦b≦40
．． 0 atm%, 0.01≦c≦30.0 atm%, 0.
002≦f≦0.3 atm%. ) High magnetic permeability amorphous alloy with excellent corrosion resistance, high strength, and high wear resistance. 2. The following formula MaYbZcNf in atomic ratio (where M is at least one transition metal element selected from Fe, Co, and Ni; Y is from Si, B, P, Ge, and Se) At least one selected metalloid element; Z is W, Mo, V, Nb, Ta, Ti, Hf, Mn,
At least one metal element selected from Cu; N is nitrogen; a, b, c and f are respectively 55.0≦a≦90.0 atm%, 10.0≦b≦40
．． 0 atm%, 0.01≦c≦30.0 atm%, 0.
002≦f≦0.3 atm%. ) A method for improving magnetic properties characterized by annealing a high magnetic permeability amorphous alloy with excellent corrosion resistance, high strength, and high wear resistance in a non-oxidizing atmosphere at a temperature below the crystallization temperature. 3. The improvement method according to claim 2, wherein the annealing is performed under a magnetic field and/or tension. 4. For annealing, cool down after annealing at 200°C/sec.
The improvement method according to claim 2 or 3, characterized in that the cooling is performed at a rate of:
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|---|---|---|---|
| JP2004575A JPH0310052A (en) | 1990-01-16 | 1990-01-16 | High permeability amorphous alloy having high corrosion resistance, high strength, and high wear resistance and improvement of magnetic property of same |
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|---|---|---|---|
| JP60227036A Division JPS6286146A (en) | 1985-10-14 | 1985-10-14 | High permeability amorphous alloy having high corrosion resistance, strength and wear resistance and method for modifying magnetic characteristic of said alloy |
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ID=11587834
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004510887A (en) * | 2000-10-02 | 2004-04-08 | ヴァキュームシュメルツェ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Annealed amorphous alloy for magnetoacoustic markers |
| CN102776452A (en) * | 2012-08-24 | 2012-11-14 | 南昌航空大学 | Iron-based amorphous alloy material with high glass-forming capability |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57137451A (en) * | 1981-02-17 | 1982-08-25 | Allegheny Ludlum Ind Inc | Amorphous metal alloy strip and manufacture |
| JPS6277464A (en) * | 1985-07-03 | 1987-04-09 | ザ スタンダ−ド オイル カンパニ− | Production of multiple metal amorphous alloy film |
-
1990
- 1990-01-16 JP JP2004575A patent/JPH0310052A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57137451A (en) * | 1981-02-17 | 1982-08-25 | Allegheny Ludlum Ind Inc | Amorphous metal alloy strip and manufacture |
| JPS6277464A (en) * | 1985-07-03 | 1987-04-09 | ザ スタンダ−ド オイル カンパニ− | Production of multiple metal amorphous alloy film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004510887A (en) * | 2000-10-02 | 2004-04-08 | ヴァキュームシュメルツェ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Annealed amorphous alloy for magnetoacoustic markers |
| CN102776452A (en) * | 2012-08-24 | 2012-11-14 | 南昌航空大学 | Iron-based amorphous alloy material with high glass-forming capability |
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