JP2005298858A - HIGH STRENGTH Ni BASED METAL GLASS ALLOY - Google Patents
HIGH STRENGTH Ni BASED METAL GLASS ALLOY Download PDFInfo
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本発明は、大きな非晶質形成能を有し、機械的性質に優れたＮｉ基金属ガラス合金に関するものである。 The present invention relates to a Ni-based metallic glass alloy having a large amorphous forming ability and excellent mechanical properties.
溶融状態の合金を急冷することにより、薄帯状、フィラメント状、粉粒体状など、種々の形状を有する非晶質（アモルファス）合金が得られることがよく知られている。非晶質合金薄帯は、大きな急冷速度の得られる単ロール法、双ロール法、回転液中紡糸法、アトマイズ法などの種々の方法で作製できるので、これまでにもＦｅ系、Ｔｉ系、Ｃｏ系、Ｚｒ系、Ｃｕ系、Ｐｄ系又はＮｉ系について多くの非晶質合金が得られており、優れた機械的性質、高い耐腐食性等の非晶質合金特有の性質が明らかにされた。 It is well known that an amorphous alloy having various shapes such as a ribbon shape, a filament shape, and a granular material shape can be obtained by rapidly cooling a molten alloy. Amorphous alloy ribbons can be produced by various methods such as a single roll method, a twin roll method, a spinning in a rotating liquid method, an atomizing method and the like that can obtain a large quenching rate. Many amorphous alloys have been obtained for Co, Zr, Cu, Pd, or Ni, and the properties unique to amorphous alloys such as excellent mechanical properties and high corrosion resistance have been clarified. It was.
例えば、Ｎｉ基非晶質合金では、Ｎｉ-Ｐｄ-Ｓｉ-Ｂ-Ａｌ合金(特許文献１)、Ｎｉ-Ｐ-Ｂ合金（ 特許文献２）、ＲｒＮｉｓＴｔ系高硬度合金（Ｒは、Ｔａ、Ｎｂ、又はＷの１種以上、Ｔは、Ｔｉ又はＺｒの１種以上、ｒは、３５〜６５原子％、ｓは、２５〜６５原子％、ｔは、１５原子％以下、ｒ、ｓ、ｔの合計は１００）(特許文献３)、Ｔａ−Ｎｉ，Ｔａ−（Ｔｉ，Ｎｂ，Ｗ）−Ｎｉ系高耐食性合金(特許文献４)などが知られている。 For example, in a Ni-based amorphous alloy, a Ni—Pd—Si—B—Al alloy (Patent Document 1), a Ni—P—B alloy (Patent Document 2), a R r Ni s Tt high hardness alloy (R Is one or more of Ta, Nb, or W, T is one or more of Ti or Zr, r is 35 to 65 atomic%, s is 25 to 65 atomic%, t is 15 atomic% or less, The total of r, s, and t is 100) (Patent Document 3), Ta-Ni, Ta- (Ti, Nb, W) -Ni high corrosion resistance alloy (Patent Document 4), and the like are known.
しかし、これらのＮｉ基非晶質合金は液体急冷法により薄帯状、粉末状、細線状などのものしか得られていない。そして、高い熱的安定性を示しておらず、最終製品形状へ加工することも困難なことから、工業的に見て、その用途がかなり限定されていた。 However, these Ni-based amorphous alloys have only been obtained in the form of strips, powders, fine wires, etc. by the liquid quenching method. And since it does not show high thermal stability and it is difficult to process it into a final product shape, its use is considerably limited from an industrial viewpoint.
アモルファス合金をバルク状で作るという夢を実現したのが「金属ガラス」である。すなわち、ガラス形成能が非常に高い合金が１９８０年代にＰｄ-Ｓｉ-Ｃｕ合金で見出だされた。さらに、１９９０年になってから、実用的な合金組成でガラス形成能が非常に高い合金が見出された。一般に、「アモルファス合金」では加熱によりガラス転移点に到達する前に結晶化が進行してしまい、ガラス転移は実験的には観察できない。これに対して、「金属ガラス」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。 “Metallic glass” has realized the dream of making amorphous alloys in bulk. That is, an alloy having a very high glass forming ability was found in the 1980s as a Pd—Si—Cu alloy. Furthermore, since 1990, alloys with a practical alloy composition and a very high glass forming ability have been found. In general, in an “amorphous alloy”, crystallization proceeds before reaching the glass transition point by heating, and the glass transition cannot be observed experimentally. On the other hand, in the “metal glass”, 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 K.
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。 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 an oxide glass and can be easily plastically deformed (viscous flow) at a high temperature. Because.
「金属ガラス」は、非晶質形成能が高い、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すると合金の粘性が低下するために閉塞鍛造などの方法により任意形状に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、従来のアモルファス合金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、各種工業製品の材料としての有用性は非常に大きい。 “Metal glass” has a high amorphous forming ability, that is, a so-called bulk metal casting made of a glass phase and larger in size is cooled and solidified in a supercooled liquid state from a molten metal by copper mold casting or the like. It has characteristics that can be manufactured, and since it has a characteristic that it can be plastically processed into an arbitrary shape by a method such as closed forging because the viscosity of the alloy decreases when heated to a supercooled liquid state. However, it is a material that is essentially different from “amorphous alloys” such as conventional amorphous alloy ribbons and fibers, and is very useful as a material for various industrial products.
本発明者らは、先に、非晶質形成能、加工性、機械的強度に優れたＮｉ-Ｐ-Ｍ(Ｍは、Ｔｉ,Ｚｒ,Ｈｆ,Ｎｂ,又はＴａの１種以上)系Ｎｉ基金属ガラス合金を開発した（特許文献５）。また、２００３年に高いガラス安定性及び非晶質形成能に優れたＮｉ-Ｎｂ-Ｓｎ基金属ガラス合金が開発された（非特許文献１）が、このＮｉ基金属ガラス合金は非常に
脆くて、優れた機械的性質と高いガラス安定性を備えていると言えない。
The present inventors have previously described Ni-PM (M is one or more of Ti, Zr, Hf, Nb, or Ta) -based Ni excellent in amorphous forming ability, workability, and mechanical strength. A base metal glass alloy was developed (Patent Document 5). Further, in 2003, a Ni—Nb—Sn-based metallic glass alloy having high glass stability and excellent amorphous forming ability was developed (Non-patent Document 1), but this Ni-based metallic glass alloy is very brittle. It cannot be said that it has excellent mechanical properties and high glass stability.
本発明と関連するＮｉ基非晶質合金では、主に磁気的性質及び耐食性に着目した研究が行われてきた。これらのＮｉ―非金属（Ｓｉ，Ｂ，Ｐ，Ｃ）系非晶質合金は、主に上述の単ロール液体急冷法により作製された薄帯状試料で研究がなされた。しかしながら、実用的な使用に適する大形状Ｎｉ基非晶質合金、言い換えれば非晶質形成能に優れたＮｉ基金属ガラス合金に関して研究開発はあまり進んでいない。前述したＮｉ基金属ガラス合金は高い熱的安定性、大きなガラス形成能、優れた加工性、優れた機械的性質を兼ね備えていなかった。 In the Ni-based amorphous alloys related to the present invention, research mainly focusing on magnetic properties and corrosion resistance has been conducted. These Ni-nonmetal (Si, B, P, C) amorphous alloys have been studied mainly with thin strip samples prepared by the single-roll liquid quenching method described above. However, research and development have not progressed so far with respect to large-shaped Ni-based amorphous alloys suitable for practical use, in other words, Ni-based metallic glass alloys with excellent amorphous forming ability. The aforementioned Ni-based metallic glass alloys did not have high thermal stability, large glass forming ability, excellent workability, and excellent mechanical properties.
そこで、本発明者らは、上述の課題を解決するために、大きな非晶質形成能を有し、優れた加工性、機械的性質を兼ね備えたＮｉ基金属ガラス合金を提供することを目的として、最適組成について研究した結果、Ｎｉ基からなる特定組成の合金を溶融し、液体状態から急冷凝固させることによって、４０K以上の過冷却液体領域△Txを示す上述の性能を具備したＮｉ基金属ガラス合金が得られることを見出し、本発明を完成するに至った。 Therefore, in order to solve the above-mentioned problems, the present inventors have aimed to provide a Ni-based metallic glass alloy having a large amorphous forming ability and having excellent workability and mechanical properties. As a result of studying the optimum composition, a Ni-based metallic glass having the above-described performance exhibiting a supercooled liquid region ΔTx of 40K or more by melting an alloy having a specific composition comprising Ni-base and rapidly solidifying it from a liquid state. The inventors have found that an alloy can be obtained and have completed the present invention.
すなわち、本発明は、下記の組成式で示されるＮｉ基金属ガラス合金である。
（１）式 ： Ｎｉ１００−ａ−ｂ−ｃＴａａＴｉｂ(Ｚｒ,Ｈｆ)ｃ［式中、ａ,ｂ,ｃは原子％で、５原子％≦ａ≦３５原子％、５原子％≦ｂ＜３５原子％、かつ１５原子％≦ａ＋ｂ＜４０原子％、０原子％＜ｃ≦２０原子％であり、かつ３０原子％≦ａ＋ｂ＋ｃ≦５５原子％、を満足する。］で示される組成を有する、非晶質相を体積百分率で８０％以上含む、圧縮強度が２８００MPa以上の高強度のＮｉ基金属ガラス合金。
That is, the present invention is a Ni-based metallic glass alloy represented by the following composition formula.
(1) Formula: Ni 100- abc Ta a Ti b (Zr, Hf) c [wherein a, b, c are atomic%, 5 atomic% ≦ a ≦ 35 atomic%, 5 atomic% ≦ b <35 atomic%, 15 atomic% ≦ a + b <40 atomic%, 0 atomic% <c ≦ 20 atomic%, and 30 atomic% ≦ a + b + c ≦ 55 atomic% are satisfied. ] A high-strength Ni-based metallic glass alloy having a composition represented by the above and containing an amorphous phase in a volume percentage of 80% or more and a compressive strength of 2800 MPa or more.
（２） 式 ：Ｎｉ１００−ａ−ｂ−ｃ−ｄＴａａＴｉｂ Ｎｂｄ［式中、ａ,ｂ,ｃは原子％で、５原子％≦ａ≦３５原子％、５原子％≦ｂ＜３５原子％、かつ１５原子％≦ａ＋ｂ＜４０原子％、０原子％＜ｄ＜３５原子％であり、かつ３０原子％≦ａ＋ｂ＋ｄ≦５５原子％、を満足する。］で示される組成を有する、非晶質相を体積百分率で８０％以上含む、圧縮強度が２８００MPa以上の高強度のＮｉ基金属ガラス合金。 (2) Formula: Ni 100-a-b-cd Ta a Ti b Nb d [wherein a, b, c are atomic%, 5 atomic% ≦ a ≦ 35 atomic%, 5 atomic% ≦ b <35 atomic%, 15 atomic% ≦ a + b <40 atomic%, 0 atomic% <d <35 atomic%, and 30 atomic% ≦ a + b + d ≦ 55 atomic% are satisfied. ] A high-strength Ni-based metallic glass alloy having a composition represented by the above and containing an amorphous phase in a volume percentage of 80% or more and a compressive strength of 2800 MPa or more.
（３）式 ：Ｎｉ１００−ａ−ｂ−ｃ−ｄ−ｅ−ｆＴａａＴｉｂ (Ｚｒ,Ｈｆ)ｃＮｂｄＭｅＴｆ［式中、Ｍは、Ｆｅ、Ｃｏ、Ｃｕ、Ｍｎよりなる群から選択される１種又は２種以上の元素、Ｔは、Ｇｅ,Ｓｎ,Ｓｉ,Ｂｅ,Ｂ,Ａｌ,Ａｇ,Ｐｄ,Ｐｔ,Ａｕ又は希土類元素よりなる群から選択される１種又は２種以上の元素であり、ａ, ｂ, ｃ, ｄ, ｅ, ｆは原子％で、５原子％≦ａ≦３５原子％、５原子％≦ｂ＜３５原子％、かつ１５原子％≦ａ＋ｂ＜４０原子％、０原子％＜ｃ≦２０原子％、０原子％≦ｄ＜３５原子％であり、０原子％≦ｅ≦２０原子％、０原子％≦ｆ≦５原子％、かつ３０原子％≦ａ＋ｂ ＋ｃ＋ｄ＋ｅ＋ｆ≦ ５５原子％、を満足する。］で示される組成を有する、非晶質相を体積百分率で８０％以上含む、圧縮強度が２８００MPa以上の高強度のＮｉ基金属ガラス合金。 (3): Ni 100-a-b- c-d-e-f Ta a Ti b (Zr, Hf) c Nb d M e T f [ wherein, M is, Fe, Co, Cu, from Mn One or two or more elements selected from the group consisting of T, one selected from the group consisting of Ge, Sn, Si, Be, B, Al, Ag, Pd, Pt, Au or rare earth elements or A, b, c, d, e, f are atomic%, 5 atomic% ≦ a ≦ 35 atomic%, 5 atomic% ≦ b <35 atomic%, and 15 atomic% ≦ a + b. <40 atomic%, 0 atomic% <c ≦ 20 atomic%, 0 atomic% ≦ d <35 atomic%, 0 atomic% ≦ e ≦ 20 atomic%, 0 atomic% ≦ f ≦ 5 atomic%, and 30 atomic % ≦ a + b + c + d + e + f ≦ 55 atomic%. ] A high-strength Ni-based metallic glass alloy having a composition represented by the above and containing an amorphous phase in a volume percentage of 80% or more and a compressive strength of 2800 MPa or more.
本発明のＮｉ基金属ガラス合金は、 △Tx＝Tx-Tg（ただし、Txは、結晶化開始温度、Tg
はガラス遷移温度を示す。）の式で表わされる過冷却液体領域△Txが４０K以上である。また、Tg/Tｌ（ただし、Tｌは、合金の液相線温度を示す。）の式で表わされる換算ガラス化温度が０.５６以上である。本発明のＮｉ基金属ガラス合金は、 金型鋳造法により直径又は厚さ０.５mm以上で、非晶質相の体積比率８０％以上の棒材又は板材が得られる。本発明のＮｉ基金属ガラス合金は、圧縮強度２８００MPa以上、硬度Hvが７５０以上であり、機械的性質に優れている。
The Ni-based metallic glass alloy of the present invention has ΔTx = Tx-Tg (where Tx is the crystallization start temperature, Tg
Indicates the glass transition temperature. The supercooled liquid region ΔTx represented by the formula Moreover, the conversion vitrification temperature represented by the formula of Tg / Tl (where Tl represents the liquidus temperature of the alloy) is 0.56 or more. The Ni-based metallic glass alloy of the present invention can be obtained by a die casting method as a bar or plate having a diameter or thickness of 0.5 mm or more and an amorphous phase volume ratio of 80% or more. The Ni-based metallic glass alloy of the present invention has a compressive strength of 2800 MPa or more and a hardness Hv of 750 or more, and is excellent in mechanical properties.
なお、本明細書中の「過冷却液体領域」とは、毎分４０Kの加熱速度で示差走査熱量分析を行うことにより得られるガラス遷移温度Tgと結晶化開始温度Txの温度間隔で定義されるものである。「過冷却液体領域」は結晶化に対する抵抗力、すなわち非晶質の安定性及び加工性を示す数値である。本合金は４０K以上の過冷却液体領域△Txを有する。また、本明細書中の「換算ガラス化温度」とは、ガラス遷移温度（Tg）と毎分５Kの加熱速度で示差熱量分析（DTA）を行うことにより得られる合金液相線温度（Tl）の比で定義されるものである。「換算ガラス化温度」は非晶質形成能力を示す数値である。 The “supercooled liquid region” in this specification is defined by the temperature interval between the glass transition temperature Tg and the crystallization start temperature Tx obtained by performing differential scanning calorimetry at a heating rate of 40 K / min. Is. The “supercooled liquid region” is a numerical value indicating resistance to crystallization, that is, amorphous stability and workability. This alloy has a supercooled liquid region ΔTx of 40K or more. The “equivalent vitrification temperature” in the present specification means an alloy liquidus temperature (Tl) obtained by performing differential calorimetry (DTA) at a glass transition temperature (T g ) and a heating rate of 5 K / min. ). The “converted vitrification temperature” is a numerical value indicating the amorphous forming ability.
本発明で規定する合金の組成範囲において、０.２mm２以上の断面積の線状金属ガラス合金塊又は０.１mm以上の厚さの板状金属ガラス合金が容易に得られる。金属元素より構成される合金は非晶質化することにより一般にその機械的性質が向上するが、本発明のＮｉ基金属ガラス合金において、塊状試料で、２８００MPaを超える圧縮強度を持つものが容易に得られ、塑性伸びを示した。本発明のＮｉ基ガラス合金から、製造される塊状試料は具体的には、断面積が０.２mm２以上、圧縮強度が２８００MPa以上である。なお、リボン試料の引張強度は圧縮強度と同程度である。 In the composition range of the alloy specified in the present invention, a linear metal glass alloy block having a cross-sectional area of 0.2 mm 2 or more or a plate-like metal glass alloy having a thickness of 0.1 mm or more can be easily obtained. An alloy composed of a metal element generally improves its mechanical properties by making it amorphous. However, in the Ni-based metallic glass alloy of the present invention, a massive sample having a compressive strength exceeding 2800 MPa can be easily obtained. Obtained and exhibited plastic elongation. Specifically, the bulk sample produced from the Ni-based glass alloy of the present invention has a cross-sectional area of 0.2 mm 2 or more and a compressive strength of 2800 MPa or more. The tensile strength of the ribbon sample is about the same as the compressive strength.
本発明のＮｉ基合金組成は、４０K以上の過冷却液体領域を示すことから大きな非晶質形成能を有し、金型鋳造法により厚さ１mm以上の板状材料又は直径１mm以上の棒状材料を容易に作製することができる。また、高強度、高硬度を有する。これらのことから、本発明は、優れた加工性、優れた機械的性質及び耐食性を兼備した実用上有用なＮｉ基金属ガラス合金を提供することができる。 Since the Ni-based alloy composition of the present invention exhibits a supercooled liquid region of 40K or more, it has a large amorphous forming ability, and a plate-like material having a thickness of 1 mm or more or a rod-like material having a diameter of 1 mm or more by a die casting method. Can be easily manufactured. Moreover, it has high strength and high hardness. From these facts, the present invention can provide a practically useful Ni-based metallic glass alloy having excellent workability, excellent mechanical properties and corrosion resistance.
以下に本発明の実施の形態を説明する。本発明のＮｉ基ガラス合金において、Ｔａ、Ｔｉは、本発明の合金の基幹となる元素群であり、特に非晶質を形成する基本となる元素である。Ｔａは、５原子％以上３５原子％以下で、好ましくは５原子％以上３０原子％以下、さらに好ましくは５原子％以上２５原子％以下である。Ｔｉは、５原子％以上３５原子％以下で、好ましくは５原子％以上３０原子％以下、さらに好ましくは５原子％以上２０原子％以下である。これらの元素は合計で１５原子％以上４０原子％未満、好ましくは２０原子％以上３５原子％以下とする。上記の組成範囲を外れると非晶質形成能が低下する。 Embodiments of the present invention will be described below. In the Ni-based glass alloy of the present invention, Ta and Ti are a group of elements that form the basis of the alloy of the present invention, and are particularly basic elements that form an amorphous state. Ta is 5 atom% or more and 35 atom% or less, preferably 5 atom% or more and 30 atom% or less, more preferably 5 atom% or more and 25 atom% or less. Ti is 5 atom% or more and 35 atom% or less, preferably 5 atom% or more and 30 atom% or less, more preferably 5 atom% or more and 20 atom% or less. The total amount of these elements is 15 atomic percent or more and less than 40 atomic percent, preferably 20 atomic percent or more and 35 atomic percent or less. Outside the above composition range, the amorphous forming ability decreases.
また、Ｚｒ、Ｈｆ元素は、Ｔａ、Ｔｉとの合計で３０原子％以上５５原子％以下、より好ましくは３５原子％以上５５原子％以下の範囲でＮｉ-Ｔａ-Ｔｉ系合金の非晶質形成能を高める効果を有する。Ｚｒ、Ｈｆ元素量は、合計で２０原子％以下で、好ましくは２.５原子％以上１５原子％以下である。 Further, the Zr and Hf elements are formed in a total amount of Ta and Ti in the range of 30 atomic% to 55 atomic%, more preferably in the range of 35 atomic% to 55 atomic%. Has the effect of enhancing performance. The total amount of Zr and Hf elements is 20 atomic% or less, preferably 2.5 atomic% or more and 15 atomic% or less.
Ｎｂは、Ｔａ、Ｔｉ元素との合計で３０原子％以上５５原子％以下、より好ましくは３５原子％以上５５原子％以下の範囲でＮｉ- Ｔａ-Ｔｉ系合金の非晶質形成能を高める効果を有する。Ｎｂは、３５原子％以下で、好ましくは５原子％以上３０原子％以下である。 Nb has an effect of enhancing the amorphous-forming ability of the Ni-Ta-Ti alloy in the range of 30 atomic% to 55 atomic%, more preferably 35 atomic% to 55 atomic% in total with Ta and Ti elements. Have Nb is 35 atomic% or less, preferably 5 atomic% or more and 30 atomic% or less.
Ｎｉは２０原子％まではＦｅ、Ｃｏ、Ｃｕ、Ｍｎよりなる群から選択される１種又は２種以上の式中Ｍで示す元素によって置換することにより、合金液相線温度（Tl）が下がり、非晶質形成能は増大するが、２０原子％を超えると過冷却液体領域△Txが小さくなり非晶質形成能が低下する。 Ni is replaced by an element represented by M in one or more of the formulas selected from the group consisting of Fe, Co, Cu, and Mn up to 20 atomic%, thereby lowering the alloy liquidus temperature (Tl). Although the amorphous forming ability increases, when it exceeds 20 atomic%, the supercooled liquid region ΔTx becomes small and the amorphous forming ability is lowered.
少量のＧｅ、Ｓｎ、Ｓｉ、Ｂｅ、Ｂ、Ａｌ、Ａｇ、Ｐｄ、Ｐｔ、Ａｕ又は希土類元素よりなる群から選択される１種又は２種以上の式中Ｔで示す元素の添加は過冷却液体領域△Txは増大するが、５原子％を超えると非晶質形成能が劣化するため、添加する場合は５原子％以下とする。これらの元素は、Ｔａ、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ元素との合計で３０原子％以上５５原子％以下、より好ましくは３５原子％以上５５原子％以下の範囲とする。少量のＣｒ、Ｖ、Ｍｏ、Ｗの添加は強度の向上に有効であるが、非晶質形成能が劣化するため、添加する場合は５原子％以下とする。 A small amount of Ge, Sn, Si, Be, B, Al, Ag, Pd, Pt, Au, or one or two or more elements selected from the group consisting of rare earth elements is added in the supercooled liquid. The region ΔTx increases, but if it exceeds 5 atomic%, the amorphous forming ability deteriorates. These elements are in the range of 30 atomic% to 55 atomic%, more preferably 35 atomic% to 55 atomic% in total with the Ta, Ti, Zr, Hf, and Nb elements. The addition of a small amount of Cr, V, Mo, W is effective for improving the strength, but the amorphous forming ability deteriorates.
本発明のＮｉ基ガラス合金は、溶融状態から公知の単ロール法、双ロール法、回転液中紡糸法、アトマイズ法などの種々の方法で冷却凝固させ、薄帯状、フィラメント状、粉粒体状の非晶質固体を得ることができる。また、本発明のＮｉ基金属ガラス合金は大きな非晶質形成能を有するため、上述の公知の製造方法のみならず、溶融金属を金型に充填鋳造することにより任意の形状の金属ガラス合金製品を得ることもできる。例えば、代表的な金型鋳造法においては、合金を石英管中でアルゴン雰囲気中において溶融した後、溶融金属を０.５〜１.５kg・f/cm２の噴出圧で銅製の金型内に充填凝固させることにより金属ガラス合金塊を得ることができる。更に、ダイカストキャスティング法及びスクイズキャスティング法などの製造方法を適用することもできる。 The Ni-based glass alloy of the present invention is cooled and solidified from a molten state by various methods such as a known single roll method, twin roll method, spinning in a rotating liquid, atomizing method, etc. An amorphous solid can be obtained. Further, since the Ni-based metallic glass alloy of the present invention has a large amorphous forming ability, not only the above-mentioned known production method but also a metallic glass alloy product of any shape by filling and casting molten metal into a mold You can also get For example, in a typical mold casting method, an alloy is melted in a quartz tube in an argon atmosphere, and then the molten metal is injected into a copper mold at an ejection pressure of 0.5 to 1.5 kg · f / cm 2 . A metallic glass alloy lump can be obtained by filling and solidifying. Furthermore, a manufacturing method such as a die casting method and a squeeze casting method can also be applied.
以下、本発明の実施例について説明する。表１に示す合金組成からなる材料（実施例１〜１５）について、アーク溶解法により原料合金を溶製した。これらの合金を石英管中でアルゴン雰囲気中に１６００〜１８００Kの温度で再溶融した後、溶融金属を０.２〜０.５kg・f/cm２の噴出圧で回転速度が４０m/sの銅製のロールの表面に噴射する（単ロール液体急冷法）ことによって幅約１ｍｍで厚さ約２０μmの薄帯試料を作製した。また、銅金型鋳造法によって直径１ｍｍ、長さ約４０ｍｍの棒状試料を作製した。 Examples of the present invention will be described below. About the material (Examples 1-15) which consists of an alloy composition shown in Table 1, the raw material alloy was melted by the arc melting method. These alloys are remelted in a quartz tube in an argon atmosphere at a temperature of 1600 to 1800 K, and the molten metal is made of copper with a jet pressure of 0.2 to 0.5 kg · f / cm 2 and a rotational speed of 40 m / s. A thin ribbon sample having a width of about 1 mm and a thickness of about 20 μm was produced by spraying onto the surface of a roll of (a single roll liquid quenching method). Further, a rod-shaped sample having a diameter of 1 mm and a length of about 40 mm was produced by a copper mold casting method.
実施例１〜１５、比較例１、３、５は直径１mmの棒状試料であり、比較例２、４、６は薄帯試料である。そして、薄帯試料のガラス遷移温度(Tg)、結晶化開始温度(Tx)を示差走査熱量計（DSC）より測定した。これらの値より過冷却液体領域(Tx-Tg)を算出した。液相線温度（Tｌ）の測定は、示査熱分析（DTA）により測定した。これらの値より換算ガラス化温度（Tg/Tｌ）を算出した。 Examples 1 to 15 and Comparative Examples 1, 3, and 5 are rod-shaped samples having a diameter of 1 mm, and Comparative Examples 2, 4, and 6 are ribbon samples. The glass transition temperature (T g ) and crystallization start temperature (T x ) of the ribbon sample were measured with a differential scanning calorimeter (DSC). The supercooled liquid region (T x -T g ) was calculated from these values. The liquidus temperature (Tl) was measured by differential thermal analysis (DTA). The conversion vitrification temperature (Tg / Tl) was calculated from these values.
また、金型鋳造法により作製した直径１mmの棒状試料の非晶質化の確認はＸ線回折法により行った。また、試料中に含まれる非晶質相の体積比率（Ｖｆ−ａｍｏ．）は、DSCを用いて結晶化の際の発熱量を完全非晶質化した厚さ約２０μmの薄帯との比較により評価した。これらの評価結果を表１に示す。さらに、圧縮試験片を作製し、インストロン型試験機を用いて圧縮試験を行い圧縮強度(σf)を評価した。また、ビッカース硬さHv（荷重、時間はそれぞれ２５グラム、１５秒である）を測定した。評価結果を表１に示す。
表１より明らかなように、実施例１〜１５の金属ガラス合金は、４０ K以上の過冷却液体領域と０.５６以上の換算ガラス化温度を示すとともに、直径１mmの金属ガラス合金棒が容易に得られた。図１、図２には、それぞれ実施例１（Ｎｉ６０Ｔａ２０Ｔｉ１０Ｚｒ１０）の金属ガラス合金のDSC曲線及びＸ−線回折図形を示す。実施例１〜１５の合金は
非晶質相を体積百分率で８０％以上含むが、比較例４の合金は、Ｃｏ量が２０原子％を超え、大きなガラス形成能を持っておらず、直径１mmの棒状金属ガラス合金が得られなかった。比較例５、６の合金は、本発明の合金組成の基本元素の一つであるＴｉを含有しておらず、直径１mmの棒状金属ガラス合金が得られなかった。
As is apparent from Table 1, the metal glass alloys of Examples 1 to 15 show a supercooled liquid region of 40 K or more and a converted vitrification temperature of 0.56 or more, and a metal glass alloy rod having a diameter of 1 mm is easy. Was obtained. 1 and 2 show a DSC curve and an X-ray diffraction pattern of the metal glass alloy of Example 1 (Ni 60 Ta 20 Ti 10 Zr 10 ), respectively. Although the alloys of Examples 1 to 15 contain an amorphous phase of 80% or more by volume, the alloy of Comparative Example 4 has a Co content exceeding 20 atomic%, does not have a large glass forming ability, and has a diameter of 1 mm. No rod-shaped metallic glass alloy was obtained. The alloys of Comparative Examples 5 and 6 did not contain Ti which is one of the basic elements of the alloy composition of the present invention, and a rod-shaped metallic glass alloy having a diameter of 1 mm was not obtained.
また、表１より明らかなように、実施例１〜１５の金属ガラス合金は、２８００MPa以上の圧縮破断強度及び７５０Hv以上のビッカース硬度を示す。これに対して、比較例１の合金は、Ｔａを含有しておらず、強度が２８００MPa未満になる。比較例２の合金は、Ｔａ、Ｔｉを含有しておらず非晶質形成能を有しない。比較例３の合金は、非常に脆く、加工性が悪い。図３には、実施例１（Ｎｉ６０Ｔａ２０Ｔｉ１５Ｚｒ５）の合金の圧縮試験の応力−歪み曲線を示す。図３に示されるように、本発明の合金は塑性伸びを示し、優れた加工性を有することが分かる。 Moreover, as is clear from Table 1, the metal glass alloys of Examples 1 to 15 exhibit a compression fracture strength of 2800 MPa or more and a Vickers hardness of 750 Hv or more. On the other hand, the alloy of Comparative Example 1 does not contain Ta and has a strength of less than 2800 MPa. The alloy of Comparative Example 2 does not contain Ta and Ti and does not have an amorphous forming ability. The alloy of Comparative Example 3 is very brittle and has poor workability. 3 shows, in Example 1 (Ni 60 Ta 20 Ti 15 Zr 5) of the compression test of the alloy of the stress - showing a strain curve. As shown in FIG. 3, it can be seen that the alloy of the present invention exhibits plastic elongation and has excellent workability.
本発明のＮｉ基金属ガラス合金は、強度と耐磨耗性が要求される小型精密機器部品及び耐食性が要求される配管、燃料電池用メタルセパレータなどに適する特性を有している。 The Ni-based metallic glass alloy of the present invention has characteristics suitable for small precision equipment parts that require strength and wear resistance, pipes that require corrosion resistance, metal separators for fuel cells, and the like.
Claims (3)
５原子％≦ａ≦３５原子％、
５原子％≦ｂ＜３５原子％、かつ
１５原子％≦ａ＋ｂ＜４０原子％、
０原子％＜ｃ≦２０原子％であり、かつ
３０原子％≦ａ＋ｂ＋ｃ≦５５原子％、
を満足する。］で示される組成を有する、非晶質相を体積百分率で８０％以上含む、圧縮強度が２８００MPa以上の高強度のＮｉ基金属ガラス合金。 Formula: Ni 100- abc Ta a Ti b (Zr, Hf) c [wherein a, b, c are atomic%,
5 atomic% ≦ a ≦ 35 atomic%,
5 atomic% ≦ b <35 atomic% and 15 atomic% ≦ a + b <40 atomic%,
0 atomic% <c ≦ 20 atomic% and 30 atomic% ≦ a + b + c ≦ 55 atomic%,
Satisfied. ] A high-strength Ni-based metallic glass alloy having a composition represented by the above and containing an amorphous phase in a volume percentage of 80% or more and a compressive strength of 2800 MPa or more.
５原子％≦ａ≦３５原子％、
５原子％≦ｂ＜３５原子％、かつ
１５原子％≦ａ＋ｂ＜４０原子％、
０原子％＜ｄ＜３５原子％であり、かつ
３０原子％≦ａ＋ｂ＋ｄ≦５５原子％、
を満足する。］で示される組成を有する、非晶質相を体積百分率で８０％以上含む、圧縮強度が２８００MPa以上の高強度のＮｉ基金属ガラス合金。 Formula: Ni 100-a-bc-d Ta a Ti b Nb d [wherein a, b, c are atomic%,
5 atomic% ≦ a ≦ 35 atomic%,
5 atomic% ≦ b <35 atomic% and 15 atomic% ≦ a + b <40 atomic%,
0 atomic% <d <35 atomic% and 30 atomic% ≦ a + b + d ≦ 55 atomic%,
Satisfied. ] A high-strength Ni-based metallic glass alloy having a composition represented by the above and containing an amorphous phase in a volume percentage of 80% or more and a compressive strength of 2800 MPa or more.
ａ, ｂ, ｃ, ｄ, ｅ, ｆは原子％で、
５原子％≦ａ≦３５原子％、
５原子％≦ｂ＜３５原子％、かつ
１５原子％≦ａ＋ｂ＜４０原子％、
０原子％＜ｃ≦２０原子％、
０原子％≦ｄ＜３５原子％であり、
０原子％≦ｅ≦２０原子％、
０原子％≦ｆ≦５原子％、かつ
３０原子％≦ａ＋ｂ ＋ｃ＋ｄ＋ｅ＋ｆ≦ ５５原子％、
を満足する。］で示される組成を有する、非晶質相を体積百分率で８０％以上含む、圧縮強度が２８００MPa以上の高強度のＮｉ基金属ガラス合金。
Formula: Ni 100-ab-c-d-ef Ta a Ti b (Zr, Hf) c Nb d Me T f [wherein, M is from the group consisting of Fe, Co, Cu, Mn One or more selected elements, T is one or more selected from the group consisting of Ge, Sn, Si, Be, B, Al, Ag, Pd, Pt, Au, or rare earth elements Elements of
a, b, c, d, e, f are atomic%,
5 atomic% ≦ a ≦ 35 atomic%,
5 atomic% ≦ b <35 atomic% and 15 atomic% ≦ a + b <40 atomic%,
0 atomic% <c ≦ 20 atomic%,
0 atomic% ≦ d <35 atomic%,
0 atomic% ≦ e ≦ 20 atomic%,
0 atomic% ≦ f ≦ 5 atomic% and 30 atomic% ≦ a + b + c + d + e + f ≦ 55 atomic%,
Satisfied. ] A high-strength Ni-based metallic glass alloy having a composition represented by the above and containing an amorphous phase in a volume percentage of 80% or more and a compressive strength of 2800 MPa or more.
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| WO2009054077A1 (en) * | 2007-10-25 | 2009-04-30 | Tohoku University | Metallic glass alloy with resistance to highly oxidative solution and apparatus in which highly oxidative solution is handled |
| JP2010505041A (en) * | 2006-09-26 | 2010-02-18 | ラングレット，エイブラハム | Method for manufacturing an amorphous metal product |
| CN106086522A (en) * | 2016-07-19 | 2016-11-09 | 福建工程学院 | A kind of high tough nickel alloy and preparation method thereof |
| JP2018087377A (en) * | 2016-11-28 | 2018-06-07 | 財團法人工業技術研究院Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ | Corrosion resistant structure and fuel battery using the same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010505041A (en) * | 2006-09-26 | 2010-02-18 | ラングレット，エイブラハム | Method for manufacturing an amorphous metal product |
| WO2009054077A1 (en) * | 2007-10-25 | 2009-04-30 | Tohoku University | Metallic glass alloy with resistance to highly oxidative solution and apparatus in which highly oxidative solution is handled |
| JPWO2009054077A1 (en) * | 2007-10-25 | 2011-03-03 | 国立大学法人東北大学 | High oxidation resistance metal glass alloy and high oxidation solution handling equipment |
| CN106086522A (en) * | 2016-07-19 | 2016-11-09 | 福建工程学院 | A kind of high tough nickel alloy and preparation method thereof |
| JP2018087377A (en) * | 2016-11-28 | 2018-06-07 | 財團法人工業技術研究院Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ | Corrosion resistant structure and fuel battery using the same |
| US10511030B2 (en) | 2016-11-28 | 2019-12-17 | Industrial Technology Research Institute | Anti-corrosion structure and fuel cell employing the same |
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