JP2021195569A - Zirconium-based metal glass alloy - Google Patents
Zirconium-based metal glass alloy Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 85
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 83
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 239000011521 glass Substances 0.000 title claims abstract description 23
- 229910052726 zirconium Inorganic materials 0.000 title claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims description 9
- 239000010955 niobium Substances 0.000 claims abstract description 41
- 239000010936 titanium Substances 0.000 claims abstract description 39
- 239000010949 copper Substances 0.000 claims abstract description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005300 metallic glass Substances 0.000 claims description 47
- 239000013526 supercooled liquid Substances 0.000 claims description 22
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 10
- 230000007704 transition Effects 0.000 claims description 2
- 238000007496 glass forming Methods 0.000 abstract description 22
- 238000005260 corrosion Methods 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 15
- 238000000034 method Methods 0.000 description 22
- 238000005266 casting Methods 0.000 description 20
- 238000002844 melting Methods 0.000 description 17
- 230000008018 melting Effects 0.000 description 17
- 238000001816 cooling Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000007769 metal material Substances 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 210000003918 fraction a Anatomy 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/11—Making amorphous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
- C22C2200/02—Amorphous
Abstract
Description
本発明は、高ガラス形成能、高強度、高延性、高耐食性、高粘性加工性、精密鋳造性、及び高輝性を併せ持つジルコニウム（Ｚｒ）基金属ガラス合金に関する。 The present invention relates to a zirconium (Zr) -based metallic glass alloy having high glass forming ability, high strength, high ductility, high corrosion resistance, high viscosity workability, precision castability, and high brilliance.
現在、金属ガラス合金は、溶融した液体状の合金を急速に冷却することによって、周期的な構造を持たないガラス状態となる過冷却液体領域が広い非晶質合金として知られている。これらの金属ガラス合金は、優れたガラス形成能、高い反発係数、高強度、優れた鋳造性、優れた腐食特性等を有していることから、ゴルフクラブ、携帯電話のフレーム、微小機械用ギア、腕時計のケーシングなどへの応用が広がっている。
このような金属ガラス合金として、ジルコニウム基バルク金属ガラス合金（Ｚｒ基ＢＭＧ合金（ZIRCONIUM(Zr)−based Bulk Metallic Glass Alloy））が提案されている（特許文献１、２、及び３参照）
Currently, a metallic glass alloy is known as an amorphous alloy having a wide supercooled liquid region that becomes a glass state without a periodic structure by rapidly cooling a molten liquid alloy. These metallic glass alloys have excellent glass forming ability, high coefficient of restitution, high strength, excellent castability, excellent corrosion properties, etc., and therefore, therefore, golf clubs, mobile phone frames, gears for micromachines, etc. , Applications to watch casings, etc. are expanding.
As such a metallic glass alloy, a zirconium-based bulk metallic glass alloy (Zr-based BMG alloy (ZIRCONIUM (Zr) -based Bulk Metallic Glass Alloy)) has been proposed (see Patent Documents 1, 2, and 3).
特許文献１は、原子％で、５０％以上７０％以下のジルコニウム（Ｚｒ）、１５％以上３０％以下の銅（Ｃｕ）、５％以上１５％以下のアルミニウム（Ａｌ）、２％以上２０％以下の鉄（Ｆｅ）、および０．０１％を超え０．２％以下の窒素（Ｎ）を主要成分とするＺｒ基金属ガラス合金を開示している。
特許文献１に開示のＺｒ基金属ガラス合金は、アモルファス相の形成能が高く、高強度、低ヤング率を有し、経済的に製造することができるとしている。
Patent Document 1 describes zirconium (Zr) of 50% or more and 70% or less, copper (Cu) of 15% or more and 30% or less, aluminum (Al) of 5% or more and 15% or less, and 2% or more and 20% in atomic%. The following Zr-based metallic glass alloys containing iron (Fe) and nitrogen (N) of more than 0.01% and 0.2% or less are disclosed.
The Zr-based metallic glass alloy disclosed in Patent Document 1 has a high ability to form an amorphous phase, has high strength, and has a low Young's modulus, and can be economically produced.
特許文献２は、原子％で、Ｚｒ７５−ｘ−ｙ−ｚＡｌｘＮｉｙ−ａＭｚＢａ（ｘは１０≦ｘ≦１９、ｙは１５≦ｙ≦２８、ＭはＮｂ又はＴａであり、ｚは０＜ｚ≦８、ＢはＦｅ又はＣｏであり、ａは０≦ａ≦８）で示される組成を有しているＣｕを含まないＺｒ基金属ガラス合金を開示している。
特許文献２に開示のＺｒ基金属ガラス合金は、大きな非晶質形成能を有し、優れた機械的性質、加工性、及び耐食性を兼ね備えているとしている。
Patent Document 2, in atomic percent, at Zr 75-x-y-z Al x Ni y-a M z B a (x is 10 ≦ x ≦ 19, y is 15 ≦ y ≦ 28, M is Nb or Ta Yes, z is 0 <z ≦ 8, B is Fe or Co, and a is Cu-free Zr-based metallic glass alloy having the composition shown by 0 ≦ a ≦ 8).
It is said that the Zr-based metallic glass alloy disclosed in Patent Document 2 has a large amorphous forming ability, and has excellent mechanical properties, processability, and corrosion resistance.
特許文献３は、原子％で、Ｚｒ７０−８０Ｂｅ０．８−５Ｃｕ１−１５Ｎｉ１−１５Ａｌ１−５（ＮｂｙＴｉ１−ｙ）０．５−３（原子分率ｙ＝０．１〜１）、又はＺｒ７０−８０Ｂｅ０．８−５（ＣｕｘＮｉ１−ｘ）１０−２５Ａｌ１−５（ＮｂｙＴｉ１−ｙ）０．５−３（原子分率ｘ＝０．１〜０．９、ｙ＝０．１〜１）で示される組成を有しているジルコニウム系合金金属ガラスを開示している。
特許文献３に開示のジルコニウム系合金金属ガラスは、結晶化温度（Ｔｘ）とガラス転移温度（Ｔｇ）の間の温度差（ＤＴ＝ΔＴｘ）が７０Ｋ以上、例えば１２０Ｋ超であり、大きなガラス形成能を有し、５ｍｍ超、例えば８ｍｍ〜２０ｍｍの厚さを有するとしている。
特許文献４は、ＺｒａＮｉｂＣｕｃＡｌｄ（式中のａ、ｂ、ｃ、ｄは、原子％で、ａは６０〜７５原子％、ｂは１〜３０原子％、ｃは１〜３０原子％、ｄは５〜２０原子％である］で示される組成を有する高延性金属ガラス合金を開示している。
特許文献４に開示の高延性金属ガラス合金は、塑性加工性に優れ、冷間プレス加工などの金属加工プロセスに適用可能な高延性金属ガラス合金であるとしている。
Patent Document 3, in atomic%, Zr 70-80 Be 0.8-5 Cu 1-15 Ni 1-15 Al 1-5 (Nb y Ti 1-y) 0.5-3 ( atomic fraction y = 0.1), or Zr 70-80 Be 0.8-5 (Cu x Ni 1-x) 10-25 Al 1-5 (Nb y Ti 1-y) 0.5-3 ( atomic fraction A zirconium-based alloy metallic glass having a composition represented by x = 0.1 to 0.9 and y = 0.1 to 1) is disclosed.
The zirconium-based alloy metallic glass disclosed in Patent Document 3 has a temperature difference (DT = ΔTx) between the crystallization temperature (Tx) and the glass transition temperature (Tg) of 70 K or more, for example, 120 K or more, and has a large glass forming ability. It is said that it has a thickness of more than 5 mm, for example, 8 mm to 20 mm.
Patent Document 4 describes Zr a Ni b Cu c Al d (a, b, c, d in the formula are atomic%, a is 60 to 75 atomic%, b is 1 to 30 atomic%, and c is 1 to 1). 30 atomic%, d is 5 to 20 atomic%] discloses a highly ductile metallic glass alloy having the composition shown in.
The highly stretchable metallic glass alloy disclosed in Patent Document 4 is said to be a highly ductile metallic glass alloy that is excellent in plastic workability and can be applied to metal processing processes such as cold press working.
ところで、特許文献１、２、及び３に開示のＺｒ基金属ガラス合金は、個々にはガラス形成能（非晶質形成能）に優れていたり、強度等の機械的性質に優れていたり、加工性、及び耐食性等に優れていたり、塑性加工性に優れ、冷間プレス加工などの金属加工プロセスに適用可能な高延性であったりするものの、高ガラス形成能、高強度、高延性、高耐食性、高粘性加工性、精密鋳造性、及び高輝性を併せ持つものではないという問題があった。 By the way, the Zr-based metallic glass alloys disclosed in Patent Documents 1, 2 and 3 are individually excellent in glass forming ability (amorphous forming ability), excellent in mechanical properties such as strength, and processed. Although it has excellent properties and corrosion resistance, excellent plastic workability, and high ductility applicable to metal processing processes such as cold press working, it has high glass forming ability, high strength, high ductility, and high corrosion resistance. There is a problem that it does not have high viscosity workability, precision castability, and high brightness.
本発明の目的は、上記従来技術の問題点を解消し、高ガラス形成能、高強度、高延性、高耐食性、高粘性加工性、精密鋳造性、及び高輝性等の優れた特性を併せ持つジルコニウム（Ｚｒ）基金属ガラス合金を提供することにある。 An object of the present invention is to solve the above-mentioned problems of the prior art, and to combine excellent properties such as high glass forming ability, high strength, high ductility, high corrosion resistance, high viscosity workability, precision castability, and high brilliance. (Zr) is to provide a base metal glass alloy.
上記目的を達成するために、本発明は、原子％で、６２％以上６７％以下のジルコニウム（Ｚｒ）、１％以上５％以下のニオブ（Ｎｂ）、０．５％以上２％以下のチタン（Ｔｉ）、１２％以上１５％以下の銅（Ｃｕ）、８％以上１０％以下のニッケル（Ｎｉ）、及び７．５％以上８．５％以下のアルミニウム（Ａｌ）を含有し、Ｚｒ６２−６７Ｎｂ１−５Ｔｉ０．５−２Ｃｕ１２−１５Ｎｉ８−１０Ａｌ７．５−８．５で示される組成を有するジルコニウム（Ｚｒ）基金属ガラス合金を開発し、提供するものである。 In order to achieve the above object, the present invention has zirconium (Zr) of 62% or more and 67% or less, niobium (Nb) of 1% or more and 5% or less, and titanium of 0.5% or more and 2% or less in atomic%. It contains (Ti), 12% or more and 15% or less of copper (Cu), 8% or more and 10% or less of nickel (Ni), and 7.5% or more and 8.5% or less of aluminum (Al), and Zr 62. -67 Nb 1-5 Ti 0.5-2 Cu 12-15 Ni 8-10 Al A zirconium (Zr) -based metallic glass alloy having the composition shown by 7.5-8.5 has been developed and provided. be.
ここで、原子％で、Ｚｒ、Ｎｂ、及びＴｉの含有量の和（Ｚｒ＋Ｎｂ＋Ｔｉ）が、６５％以上７０％以下であることが好ましい。
また、原子％で、Ｎｂ、及びＴｉの含有量の和（Ｎｂ＋Ｔｉ）が、５％以下であり、Ｎｂ、及びＴｉの含有量の比（Ｎｂ／Ｔｉ）が、１．０以上８．０以下であることが好ましい。
また、結晶化開始温度Ｔｘとガラス転移温度Ｔｇとの差（結晶化開始温度Ｔｘ−ガラス転移温度Ｔｇ）で求められる過冷却液体領域（ΔＴｘ）が、８５Ｋ以上であることが好ましい。
また、塑性ひずみ（εｆ）が、１０％以上であることが好ましい。
Here, it is preferable that the sum of the contents of Zr, Nb, and Ti (Zr + Nb + Ti) is 65% or more and 70% or less in terms of atomic%.
In addition, the sum of the contents of Nb and Ti (Nb + Ti) is 5% or less in atomic%, and the ratio of the contents of Nb and Ti (Nb / Ti) is 1.0 or more and 8.0 or less. Is preferable.
Further, the supercooled liquid region (ΔTx) obtained by the difference between the crystallization start temperature Tx and the glass transition temperature Tg (crystallization start temperature Tx − glass transition temperature Tg) is preferably 85 K or more.
Further, the plastic strain (ε f ) is preferably 10% or more.
本発明によれば、高ガラス形成能、高強度、高延性、高耐食性、高粘性加工性、精密鋳造性、及び高輝性を併せ持つジルコニウム（Ｚｒ）基金属ガラス合金を提供することができる。 According to the present invention, it is possible to provide a zirconium (Zr) -based metallic glass alloy having high glass forming ability, high strength, high ductility, high corrosion resistance, high viscosity workability, precision castability, and high brilliance.
以下に、本発明のＺｒ基金属ガラス合金を詳細に説明する。
本発明に係るジルコニウム（Ｚｒ）基金属ガラス合金は、原子％で、６２％以上６７％以下のジルコニウム（Ｚｒ）、１％以上５％以下のニオブ（Ｎｂ）、０．５％以上２％以下のチタン（Ｔｉ）、１２％以上１５％以下の銅（Ｃｕ）、８％以上１０％以下のニッケル（Ｎｉ）、及び７．５％以上８．５％以下のアルミニウム（Ａｌ）を含有し、したがって、Ｚｒ６２−６７Ｎｂ１−５Ｔｉ０．５−２Ｃｕ１２−１５Ｎｉ８−１０Ａｌ７．５−８．５で示される組成を有するものである。
本発明のＺｒ基金属ガラス合金は、上述した各成分金属を溶解した後、臨界冷却速度以上で冷却することにより得られるものである。
Hereinafter, the Zr-based metallic glass alloy of the present invention will be described in detail.
The zirconium (Zr) -based metallic glass alloy according to the present invention has zirconium (Zr) of 62% or more and 67% or less, niobium (Nb) of 1% or more and 5% or less, and 0.5% or more and 2% or less in atomic%. Contains titanium (Ti), 12% or more and 15% or less copper (Cu), 8% or more and 10% or less nickel (Ni), and 7.5% or more and 8.5% or less aluminum (Al). Therefore, it has the composition shown by Zr 62-67 Nb 1-5 Ti 0.5-2 Cu 12-15 Ni 8-10 Al 7.5-8.5.
The Zr-based metallic glass alloy of the present invention is obtained by melting each of the above-mentioned component metals and then cooling at a critical cooling rate or higher.
本発明のＺｒ基金属ガラス合金は、高ガラス形成能、高強度、高延性、高耐食性、高粘性加工性、精密鋳造性、及び高輝性という優位な特徴を併せ持つものであるが、本発明のＺｒ基金属ガラス合金を構成する各成分金属元素は、上記所定割合で配合されることによって一体となって、上記特徴に寄与しているものである。 The Zr-based metallic glass alloy of the present invention has the advantageous features of high glass forming ability, high strength, high ductility, high corrosion resistance, high viscosity workability, precision castability, and high brilliance. Each component metal element constituting the Zr-based metallic glass alloy is integrally blended in the above-mentioned predetermined ratio, and contributes to the above-mentioned characteristics.
本発明のＺｒ基金属ガラス合金は、結晶化開始温度（以下、結晶化温度という）Ｔｘとガラス転移温度Ｔｇとの差（結晶化温度Ｔｘ−ガラス転移温度Ｔｇ）として求められる過冷却液体領域（その温度幅）（ΔＴｘ）が広く、８５Ｋ以上であることが好ましい。したがって、本発明のＺｒ基金属ガラス合金は、過冷却液体の高安定による高いガラス形成能と高粘性加工性を持つ。
ここで、高いガラス形成能は、過冷却液体領域（ΔＴｘ）が８５Ｋ以上で、広いことによるガラス相生成が容易であることを言う。また、高粘性加工性を持つとは、ガラス転移温度Ｔｇと結晶化温度Ｔｘの間の過冷却液体域ΔＴｘでは粘性が１０１３Poise（ポアズ）以下となり、水飴のように加工できる性質を持つことを言う。
The Zr-based metal glass alloy of the present invention has a supercooled liquid region (hereinafter referred to as crystallization temperature) Tx and a glass transition temperature Tg (crystallization temperature Tx-glass transition temperature Tg). The temperature range) (ΔTx) is wide, and it is preferable that the temperature is 85 K or more. Therefore, the Zr-based metallic glass alloy of the present invention has high glass forming ability and high viscosity workability due to the high stability of the supercooled liquid.
Here, the high glass forming ability means that the supercooled liquid region (ΔTx) is 85 K or more, and the glass phase can be easily formed due to the wide area. In addition, having high viscosity processability means that the viscosity is 10 13 Poise or less in the supercooled liquid region ΔTx between the glass transition temperature Tg and the crystallization temperature Tx, and it has the property of being able to be processed like a water candy. Say.
また、本発明のＺｒ基金属ガラス合金は、塑性ひずみ（εｆ）が大きく、１０％以上（εｆ≧１０％）であることが好ましい。したがって、本発明のＺｒ基金属ガラス合金は、高延性であるという特徴を持つ。
また、本発明のＺｒ基金属ガラス合金は、例えば１５００ＭＰａ以上という合金の強度と約２％の高弾性ひずみを実用上必要とされる高い強度と高いたわみ性を持つという特徴も有する。
更に、本発明のＺｒ基金属ガラス合金は、高輝性という特徴をも持つ。ここで、高輝性を持つとは、金属ガラスは原子が均一に混ざり且つ無秩序に配列しており、結晶合金にある結晶粒界や結晶方位差異を含まないために、表面が原子レベルで平滑となり、その結果、精密な鋳造反転性、高い光輝性、光反射性を示す性質を持つことを言う。
Further, the Zr-based metallic glass alloy of the present invention has a large plastic strain (ε f ) and is preferably 10% or more (ε f ≧ 10%). Therefore, the Zr-based metallic glass alloy of the present invention is characterized by high ductility.
Further, the Zr-based metallic glass alloy of the present invention is also characterized by having a strength of an alloy of, for example, 1500 MPa or more and a high elastic strain of about 2%, which is practically required to have high strength and high flexibility.
Further, the Zr-based metallic glass alloy of the present invention also has a feature of high brilliance. Here, having high brilliance means that the surface of metallic glass becomes smooth at the atomic level because the atoms are uniformly mixed and arranged in a disorderly manner and do not include the grain boundaries and crystal orientation differences in the crystal alloy. As a result, it is said to have the properties of exhibiting precise casting inversion, high brilliance, and light reflectivity.
本発明のＺｒ基金属ガラス合金の主要な成分金属について説明する。
Ｚｒは、金属ガラス合金の基となる元素であって、上述のように、その含有量は、原子％で、６２％以上でかつ６７％以下である必要がある。その結果、Ｚｒは、過冷却液体領域ΔＴｘを拡大する効果があり、ガラス形成能を高め、アモルファス相（非晶質相）を形成し易くすると共に、高い延性を示す効果がある。また、空気中で酸化皮膜や不働態被膜を形成することにより合金に耐食性を与える元素である。
The main constituent metals of the Zr-based metallic glass alloy of the present invention will be described.
Zr is an element that is the basis of a metallic glass alloy, and as described above, its content needs to be 62% or more and 67% or less in atomic%. As a result, Zr has the effect of expanding the supercooled liquid region ΔTx, enhances the glass forming ability, facilitates the formation of an amorphous phase (amorphous phase), and has the effect of exhibiting high ductility. It is also an element that imparts corrosion resistance to alloys by forming an oxide film or passivation film in the air.
Ｃｕは、金属ガラス合金の機械的特性を向上させる効果がある。Ｃｕの含有量は、上述のように、原子％で、１２％以上でかつ１５％以下であることが必要である。その理由は、Ｃｕの含有量が１２％未満の場合、あるいは１５％を超える場合には、過冷却液体領域ΔＴｘが狭くなり、合金のガラス形成能が低下すると共に、合金の強度を実用上必要とされる強度、例えば１５００ＭＰａ以上に高めることができないからである。さらに、１５％以上の高ひずみ特性が得られなくなるためでもある。 Cu has the effect of improving the mechanical properties of the metallic glass alloy. As described above, the Cu content needs to be 12% or more and 15% or less in atomic%. The reason is that when the Cu content is less than 12% or more than 15%, the supercooled liquid region ΔTx becomes narrow, the glass forming ability of the alloy decreases, and the strength of the alloy is practically required. This is because the strength cannot be increased to, for example, 1500 MPa or more. Further, it is also because the high strain characteristic of 15% or more cannot be obtained.
Ａｌは、金属ガラス合金の形成のための不可欠な元素であり、さらに耐食性を向上させる効果がある。Ａｌの含有量は、上述のように、原子％で、７．５％以上でかつ８．５原子％以下であることが必要である。その理由は、Ａｌの含有量が、７．５％未満の場合、あるいは８．５％を超える場合には、過冷却液体領域ΔＴｘが狭くなり、合金のガラス形成能が低下するようになるからである。また、Ａｌの含有量が、８．５％を超える場合には、塑性ひずみ（εｆ）が小さくなり、延性が低下するからである。 Al is an indispensable element for forming a metallic glass alloy, and has an effect of further improving corrosion resistance. As described above, the content of Al needs to be 7.5% or more and 8.5 atomic% or less in atomic%. The reason is that when the Al content is less than 7.5% or more than 8.5%, the supercooled liquid region ΔTx becomes narrow and the glass forming ability of the alloy decreases. Is. Further, when the Al content exceeds 8.5%, the plastic strain (ε f ) becomes small and the ductility decreases.
Ｎｉは、過冷却液体領域ΔＴｘを拡大し、ガラス形成能を高める効果がある。Ｎｉの含有量は、上述のように、原子％で、８％以上でかつ１０％以下であることが必要である。その理由は、Ｎｉの含有量が、８％未満の場合、あるいは１０％を超える場合には、過冷却液体領域ΔＴｘが狭くなり、合金のガラス形成能が低下すると共に、１５％以上の高ひずみが得られなくなるからである。 Ni has the effect of expanding the supercooled liquid region ΔTx and enhancing the glass forming ability. As described above, the content of Ni needs to be 8% or more and 10% or less in atomic%. The reason is that when the Ni content is less than 8% or more than 10%, the supercooled liquid region ΔTx is narrowed, the glass forming ability of the alloy is lowered, and the high strain of 15% or more is obtained. Is not possible.
Ｎｂは、過冷却液体領域ΔＴｘを拡大し、ガラス形成能を高め、機械的な強度、及び耐蝕性を増大させる効果がある。Ｎｂの含有量は、上述のように、原子％で、１％以上でかつ５％以下であることが必要である。その理由は、Ｎｂの含有量が、１％未満の場合、あるいは５％を超える場合には、過冷却液体領域ΔＴｘが狭くなり、合金のガラス形成能が低下するからである。 Nb has the effect of expanding the supercooled liquid region ΔTx, enhancing the glass forming ability, and increasing the mechanical strength and corrosion resistance. As described above, the content of Nb needs to be 1% or more and 5% or less in atomic%. The reason is that when the content of Nb is less than 1% or more than 5%, the supercooled liquid region ΔTx becomes narrow and the glass forming ability of the alloy is lowered.
Ｔｉは、Ｎｂと共存することにより、過冷却液体域△Ｔｘを拡大し、ガラス形成能を高め、機械的強度、延性および耐食性を増大させる効果がある。Ｔｉの含有量は、上述のように、原子％で、０．５％以上でかつ２％以下であることが必要である。その理由は、Ｔｉの含有量が、０．５％未満の場合、或いは２％を超える場合には、過冷却液体域△Txが狭くなり、合金のガラス形成能が低下するからである。 When Ti coexists with Nb, it has the effect of expanding the supercooled liquid region ΔTx, enhancing the glass forming ability, and increasing the mechanical strength, ductility and corrosion resistance. As described above, the Ti content needs to be 0.5% or more and 2% or less in atomic%. The reason is that when the Ti content is less than 0.5% or more than 2%, the supercooled liquid region ΔTx becomes narrow and the glass forming ability of the alloy is lowered.
本発明のＺｒ基金属ガラス合金は、上記の組成を有するものであるが、その新規な特徴は、ＮｂとＴｉとの共存が必須である点にある。ここで、原子％で、Ｎｂ、及びＴｉの含有量の和（Ｎｂ＋Ｔｉ）が５％以下であることが好ましく、Ｎｂ、及びＴｉの含有量の比（Ｎｂ／Ｔｉ）が１．０以上８．０以下であることが好ましい。 The Zr-based metallic glass alloy of the present invention has the above-mentioned composition, but a novel feature thereof is that coexistence of Nb and Ti is indispensable. Here, it is preferable that the sum of the contents of Nb and Ti (Nb + Ti) is 5% or less in atomic%, and the ratio of the contents of Nb and Ti (Nb / Ti) is 1.0 or more. It is preferably 0 or less.
したがって、本発明のＺｒ基金属ガラス合金では、周期律表でＩＶ族、及びＶ族の遷移金属であるＺｒ、Ｎｂ、及びＴｉの３元素が必須であり、Ｚｒ、Ｎｂ、及びＴｉの３元素の総量が多いことが特徴であり、３元素の総量は、原子％で、６５％以上７０％以下（６５％〜７０％）であることが好ましい。 Therefore, in the Zr-based metal glass alloy of the present invention, three elements of Zr, Nb, and Ti, which are transition metals of Group IV and Group V, are indispensable in the periodic table, and the three elements of Zr, Nb, and Ti are essential. The total amount of the three elements is large, and the total amount of the three elements is preferably 65% or more and 70% or less (65% to 70%) in atomic%.
このように、本発明のＺｒ基金属ガラス合金においては、Ｚｒ、Ｎｂ、及びＴｉの３元素が必須であり、多成分化となっていること、しかも総量が６５原子％以上であること、Ａｌ量が８．５原子％以下であること等の相乗効果により、過冷却液体域が８５K以上であること、及び塑性ひずみが１０％以上であることの好ましい特性が現れる。
その結果、上述したように、本発明のＺｒ基金属ガラス合金は、高ガラス形成能で、高延性であり、更に、高強度、高耐食性、高粘性加工性、精密鋳造性、及び高輝性である特徴をも有するが、これらに加え、合金重量の軽減化、融点の低下、耐食性の向上、耐酸化性の向上、材料コストの低下、及び合金作製の容易化を図ることができるという特徴も有する。
As described above, in the Zr-based metallic glass alloy of the present invention, the three elements Zr, Nb, and Ti are indispensable and have multiple components, and the total amount is 65 atomic% or more. Due to the synergistic effect such that the amount is 8.5 atomic% or less, preferable characteristics that the supercooled liquid region is 85 K or more and the plastic strain is 10% or more appear.
As a result, as described above, the Zr-based metallic glass alloy of the present invention has high glass forming ability, high ductility, high strength, high corrosion resistance, high viscosity workability, precision castability, and high brightness. It has certain characteristics, but in addition to these, it also has the characteristics that it is possible to reduce the weight of the alloy, lower the melting point, improve the corrosion resistance, improve the oxidation resistance, reduce the material cost, and facilitate the alloy production. Have.
本発明のＺｒ基金属ガラス合金を製造する際には、各成分金属の小塊あるいは粉末を溶解して、各成分金属の母合金の溶融物を作製後、この母合金の溶融物を、過冷却液体状態を保ったまま冷却し固化する必要がある。金属ガラス合金を冷却して製造する方法としては、銅鋳型差圧鋳造法、射出鋳造法、鍛造鋳造法、締め付け鋳造法、傾角鋳造法、又は鋳造鋳型溶液噴出法などがある。
したがって、本発明のＺｒ基金属ガラス合金は、アーク溶解法等により、上述した含有量の各成分金属から母合金を作製後、主として銅鋳型差圧鋳造法、銅鋳型射出鋳造法、銅鋳型締め付け鋳造法、銅鋳型傾角鋳造法、銅鋳型鍛造鋳造法、又は鋳造鋳型溶液噴出法などにより、直径２〜５ｍｍの円柱状棒材、若しくは厚さ２〜４ｍｍの板材として、作製することができる。
When producing the Zr-based metallic glass alloy of the present invention, a small mass or powder of each component metal is melted to prepare a melt of the mother alloy of each component metal, and then the melt of this mother alloy is supercooled. It is necessary to cool and solidify while maintaining the cooling liquid state. As a method for cooling and manufacturing a metal glass alloy, there are a copper mold differential pressure casting method, an injection casting method, a forging casting method, a tightening casting method, an inclined casting method, a casting mold solution ejection method and the like.
Therefore, the Zr-based metal glass alloy of the present invention is mainly prepared by a copper mold differential casting method, a copper mold injection casting method, and a copper mold tightening method after producing a mother alloy from each component metal having the above-mentioned contents by an arc melting method or the like. It can be produced as a columnar bar having a diameter of 2 to 5 mm or a plate having a thickness of 2 to 4 mm by a casting method, a copper mold tilt casting method, a copper mold forging casting method, a casting mold solution ejection method, or the like.
アーク溶解においては、電流を一定の値にして溶解するのではなく、出力をコントロールしながら、例えば、当初３０％〜４０％（電流１００Ａ〜２００Ａ）からスタートし、徐々に電流電圧を上昇させる。溶解中の最大電流出力６０〜７５％（電流３００Ａ〜４００Ａ程度）の間で調整し、溶解終了時は４０％〜６０％（２００Ａ〜３００Ａ）となるように行うこと、及び被溶解物と電極先端の距離が変化すること等により、電圧、及び電流が共に変化する。したがって、初期状態から溶解終了までの電圧、及び電流の変動は、例えば、２０ｇの試料溶解の際は、電圧２０Ｖ〜４０Ｖ、電流１００Ａ〜４００Ａとなる。
即ち、アーク溶解による母合金作製では、一回の各成分金属の総和量を所定量、例えば２０ｇとして、減圧アルゴンガス雰囲気下で、電圧２０Ｖ〜４０Ｖ、電流１００Ａ〜４００Ａの条件下でのアーク溶解を少なくとも４回以上繰り返して母合金を作製する。
In arc melting, the current is not melted at a constant value, but the current and voltage are gradually increased, for example, starting from 30% to 40% (current 100A to 200A) while controlling the output. Adjust the maximum current output during melting between 60 and 75% (current about 300A to 400A) so that it is 40% to 60% (200A to 300A) at the end of melting, and the object to be dissolved and the electrode. Both the voltage and the current change due to the change in the distance of the tip and the like. Therefore, the fluctuations in the voltage and current from the initial state to the end of dissolution are, for example, 20 V to 40 V in voltage and 100 A to 400 A in current when melting a 20 g sample.
That is, in the preparation of the mother alloy by arc melting, the total amount of each component metal at one time is set to a predetermined amount, for example, 20 g, and the arc melts under the conditions of a voltage of 20 V to 40 V and a current of 100 A to 400 A under a reduced pressure argon gas atmosphere. Is repeated at least 4 times to prepare a mother alloy.
銅鋳型差圧鋳造法においては、特開平０８−１０９４１９号公報に記載されているように、水冷鋳型上に金属材料を充填し、この金属材料を急激に溶融可能な上記アーク溶解を用いて金属材料を溶解後、得られた溶融金属を、ガスの差圧、あるいは重力を利用して鋳型下部より下方に設けられた縦型の水冷鋳型に瞬時に鋳込み、金属溶湯の移動速度を速くし、大きな冷却速度を得て、大型の金属ガラスを製造する。
また、銅鋳型締め付け鋳造法においては、特開平１１−２５４１９６号公報に記載されているように、ハース上に金属材料を充填し、この金属材料を溶融可能な高エネルギ熱源を用いて金属材料を溶解後、得られた融点以上の溶融金属を、冷却界面どうしを重ね合わせることなく押圧して、融点以上の溶融金属に圧縮応力および剪断応力の少なくとも一方を与えて所望の形状に変形し、変形後もしくは変形と同時に溶融金属を臨界冷却速度以上で冷却して、所望の形状のバルク状の金属ガラスを製造する。
In the copper mold differential pressure casting method, as described in Japanese Patent Application Laid-Open No. 08-109419, a metal material is filled in a water-cooled mold, and the metal material can be rapidly melted by using the above-mentioned arc melting. After melting the material, the obtained molten metal is instantly cast into a vertical water-cooled mold provided below the bottom of the mold using the differential pressure of the gas or gravity to increase the moving speed of the molten metal. Obtain a large cooling rate to produce a large metal glass.
Further, in the copper mold tightening casting method, as described in Japanese Patent Application Laid-Open No. 11-254196, a metal material is filled on the hearth, and the metal material is formed by using a high-energy heat source capable of melting the metal material. After melting, the obtained molten metal above the melting point is pressed without overlapping the cooling interfaces, and at least one of compressive stress and shear stress is applied to the molten metal above the melting point to deform and deform into a desired shape. After or at the same time as deformation, the molten metal is cooled at a critical cooling rate or higher to produce a bulk metal glass having a desired shape.
また、銅鋳型傾角鋳造法においては、特開２００９−０６８１０１号公報に記載されているように、上面が開放された溶解炉にて合金材料を溶解し、成型用のキャビティーを有する強制冷却金型内に、合金材料の溶湯を再溶解させながら傾動させて注入する傾角鋳造を行うと同時に、強制冷却金型のキャビティー内湯面の上面をほぼ覆う大きさの冷却促進を兼ねた上パンチにて、加圧冷却して、金属ガラスを製造する。
また、鋳造鋳型溶液噴出法においては、丸（φ１ｍｍ〜φ４ｍｍ）、又は角等の任意の形状を有する二つ割の鋳造用銅鋳型の注入口中央部に、圧縮ガスによる圧力（０．０１〜０．０３ＭＰａ）を利用して高周波電源等に接続された高周波コイル等を用いて石英管、又は石英るつぼ中で溶融した母合金試料を噴射する。溶融した母合金試料は、高速で銅鋳型に移動し急冷されて固化し、即ち鋳造されて、非晶質構造となる。
Further, in the copper mold tilt casting method, as described in Japanese Patent Application Laid-Open No. 2009-068101, the alloy material is melted in a melting furnace having an open upper surface, and a forced cooling metal having a cavity for molding is provided. Inclination casting is performed by tilting and injecting the molten metal of the alloy material into the mold while remelting it, and at the same time, it is used as an upper punch that promotes cooling so as to almost cover the upper surface of the molten metal in the cavity of the forced cooling mold. And pressurize and cool to manufacture metal glass.
Further, in the casting mold solution ejection method, the pressure (0.01 to ~) by the compressed gas is applied to the central portion of the injection port of the split copper mold for casting having an arbitrary shape such as a circle (φ1 mm to φ4 mm) or a corner. Using a high frequency coil or the like connected to a high frequency power source or the like using 0.03 MPa), a molten alloy sample is injected in a quartz tube or a quartz crucible. The molten mother alloy sample moves to a copper mold at high speed, is rapidly cooled and solidified, that is, cast, and becomes an amorphous structure.
こうして作製された本発明のＺｒ基金属ガラス合金のガラス合金構造は、Ｘ線回折、光学顕微鏡観察、又は透過電子顕微鏡観察等により確認することができる。
また、塑性ひずみ（εｆ）は、インストロン試験機、又はインストロン型試験機を用いて、圧縮応力―ひずみ曲線を測定し、その曲線から評価することができる。
The glass alloy structure of the Zr-based metallic glass alloy of the present invention thus produced can be confirmed by X-ray diffraction, optical microscope observation, transmission electron microscope observation, or the like.
Further, the plastic strain (ε f ) can be evaluated from the compressive stress-strain curve measured by using an Instron tester or an Instron type tester.
以上、本発明のＺｒ基金属ガラス合金について詳細に説明したが、本発明は上記実施形態に限定されず、本発明の主旨を逸脱しない範囲において、種々の改良または変更をしてもよいのはもちろんである。 Although the Zr-based metallic glass alloy of the present invention has been described in detail above, the present invention is not limited to the above embodiment, and various improvements or changes may be made without departing from the gist of the present invention. Of course.
以下、本発明に係るＺｒ基金属ガラス合金の実施例について具体的に説明するが、本発明は、この実施例によって限定されるものではない。
（実施例１〜１０、比較例１〜７）
下記表１に示す含有量の各成分金属の粉末を、当初２０％から、溶解終了時４５％となるように出力（電圧値、及び電流値）をコントロールしながらアーク溶解で溶解し、母合金の溶融物を作成後、銅鋳型吸引鋳造法により、上述したように、過冷却液体状態を保ったまま冷却し固化して、試料径２ｍｍ（最大直径３ｍｍ以上）の円柱状棒材のＺｒ基金属ガラス合金の試料を製作した。
Hereinafter, examples of the Zr-based metallic glass alloy according to the present invention will be specifically described, but the present invention is not limited to these examples.
(Examples 1 to 10, Comparative Examples 1 to 7)
The powder of each component metal having the content shown in Table 1 below is melted by arc melting while controlling the output (voltage value and current value) so that it becomes 45% at the end of melting from 20% at the beginning, and the mother alloy is melted. After preparing the melt, it is cooled and solidified while maintaining the supercooled liquid state by the copper mold suction casting method, and the Zr group of the columnar rod with a sample diameter of 2 mm (maximum diameter of 3 mm or more) is used. A sample of metal-glass alloy was produced.
こうして作製したこれらの各試料（合金）を用いて、合金構造を検査し、最大直径（ｍｍ）、ガラス転移温度Ｔｇ（Ｋ）、結晶化温度Ｔｘ（Ｋ）、過冷却液体領域ΔＴｘ（Ｋ）、降伏強度（ＭＰａ）、破壊強度（ＭＰａ）、及び塑性ひずみεｆ（％）の各項目について測定し、評価した。
その結果を、表１に示す。
Using each of these samples (alloys) thus prepared, the alloy structure was inspected, and the maximum diameter (mm), glass transition temperature Tg (K), crystallization temperature Tx (K), and supercooled liquid region ΔTx (K). , Yield strength (MPa), fracture strength (MPa), and plastic strain ε f (%) were measured and evaluated.
The results are shown in Table 1.
ここで、合金構造は、Ｘ線回折によって検査し、確認した。表１中、「ガラス相」は、ガラス（アモルファス）のみの層であることを示し、「混相」は、ガラス（アモルファス）と結晶との混相であることを示す。
また、過冷却液体領域ΔＴｘ（Ｋ）は、結晶化温度Ｔｘとガラス転移温度Ｔｇとの差（結晶化温度Ｔｘ−ガラス転移温度Ｔｇ）として求めた。
また、塑性ひずみεｆは、インストロン試験機を用いて、圧縮応力―ひずみ曲線を測定し、その曲線から評価した。
Here, the alloy structure was inspected and confirmed by X-ray diffraction. In Table 1, "glass phase" indicates that the layer is only glass (amorphous), and "mixed phase" indicates that the layer is a mixed phase of glass (amorphous) and crystals.
The supercooled liquid region ΔTx (K) was determined as the difference between the crystallization temperature Tx and the glass transition temperature Tg (crystallization temperature Tx − glass transition temperature Tg).
The plastic strain ε f was evaluated from the compressive stress-strain curve measured using an Instron tester.
表１に示すように、各元素の含有量が本発明の範囲に入る実施例１〜１０に示す試料は、いずれも、試料径が２ｍｍであり、最大直径は３ｍｍ以上、又は４ｍｍ以上と大きく、合金構造は、ガラス層であることが確認された。
また、過冷却液体領域ΔＴｘは、いずれの試料も、８５Ｋ以上であり、高ガラス形成能を持つことが分かった。
また、降伏強度は、いずれの試料も、１５００ＭＰａ以上であり、破壊強度は、いずれの試料も、１６００ＭＰａ以上であり、高強度であることが分かった。
また、塑性ひずみεｆは、いずれの試料も、１０%以上であり、高延性であることが分かった。
As shown in Table 1, the samples shown in Examples 1 to 10 in which the content of each element falls within the range of the present invention all have a sample diameter of 2 mm and a maximum diameter of 3 mm or more, or 4 mm or more. , The alloy structure was confirmed to be a glass layer.
Further, it was found that the supercooled liquid region ΔTx was 85 K or more in all the samples and had a high glass forming ability.
Further, it was found that the yield strength of each sample was 1500 MPa or more, and the fracture strength of each sample was 1600 MPa or more, which was high strength.
Further, the plastic strain ε f was 10% or more in all the samples, and it was found that they had high ductility.
一方、表１に示すように、本発明範囲を逸脱する比較例１〜７は、本発明効果を得ることができなかった。
すなわち、比較例４〜７は、合金構造がガラス層と結晶層の混相であり、金属ガラス合金になっていないものであった。比較例４〜７では、主構成相が結晶となり、明瞭なガラス転移温度Ｔｇ、及び結晶化温度Ｔｘが検出できず、過冷却液体領域ΔＴｘを算出できなかった。
また、比較例１〜７は、いずれも、塑性ひずみεｆが１０%未満であり、延性が低いことが分かった。
以上から、本発明の効果は明らかである。
On the other hand, as shown in Table 1, Comparative Examples 1 to 7 outside the scope of the present invention could not obtain the effect of the present invention.
That is, in Comparative Examples 4 to 7, the alloy structure was a mixed phase of a glass layer and a crystal layer, and the alloy was not a metallic glass alloy. In Comparative Examples 4 to 7, the main constituent phase became crystals, a clear glass transition temperature Tg and a crystallization temperature Tx could not be detected, and the supercooled liquid region ΔTx could not be calculated.
Further, in all of Comparative Examples 1 to 7, it was found that the plastic strain ε f was less than 10% and the ductility was low.
From the above, the effect of the present invention is clear.
本発明のＺｒ基金属ガラス合金は、電磁気機器フレーム、ばね材、ピン材、ギヤー材、センサー材、ミラー材、センサー材、時計ケース、時計文字盤、時計針、光学素子材、及び刃物等の用途に適用することができる。 The Zr-based metallic glass alloy of the present invention is used for electromagnetic device frames, spring materials, pin materials, gear materials, sensor materials, mirror materials, sensor materials, watch cases, watch faces, watch hands, optical element materials, cutlery, etc. It can be applied to applications.
Claims (5)
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| JP2020100401A JP2021195569A (en) | 2020-06-09 | 2020-06-09 | Zirconium-based metal glass alloy |
| CN202010956484.2A CN113774294A (en) | 2020-06-09 | 2020-09-11 | Zirconium-based metallic glass alloy |
| US17/129,262 US20210381083A1 (en) | 2020-06-09 | 2020-12-21 | Zirconium-based metal glass alloy |
| KR1020200180287A KR20210152925A (en) | 2020-06-09 | 2020-12-21 | Zirconium-based metal glass alloy |
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| JP2020100401A JP2021195569A (en) | 2020-06-09 | 2020-06-09 | Zirconium-based metal glass alloy |
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| US5735975A (en) * | 1996-02-21 | 1998-04-07 | California Institute Of Technology | Quinary metallic glass alloys |
| JPH1171661A (en) * | 1997-08-29 | 1999-03-16 | Akihisa Inoue | High strength amorphous alloy and its production |
| CN1188540C (en) * | 2001-11-09 | 2005-02-09 | 中国科学院物理研究所 | Low-density blocky metal-glass |
| JP5152790B2 (en) | 2008-03-11 | 2013-02-27 | 国立大学法人東北大学 | High ductility metallic glass alloy |
| JP2010144245A (en) | 2008-12-22 | 2010-07-01 | Tohoku Univ | Zr BASED METAL GLASS ALLOY |
| JP5685761B2 (en) | 2011-01-31 | 2015-03-18 | 株式会社真壁技研 | Zr-based metallic glass alloy containing no Cu |
| US9499891B2 (en) | 2013-08-23 | 2016-11-22 | Heraeus Deutschland GmbH & Co. KG | Zirconium-based alloy metallic glass and method for forming a zirconium-based alloy metallic glass |
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