CN1351192A - Zr-based amorphous alloy with high formation power - Google Patents
Zr-based amorphous alloy with high formation power Download PDFInfo
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- CN1351192A CN1351192A CN 00123186 CN00123186A CN1351192A CN 1351192 A CN1351192 A CN 1351192A CN 00123186 CN00123186 CN 00123186 CN 00123186 A CN00123186 A CN 00123186A CN 1351192 A CN1351192 A CN 1351192A
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- Prior art keywords
- amorphous
- alloy
- amorphous alloy
- bulk
- high formation
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- 230000015572 biosynthetic process Effects 0.000 title claims description 14
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 19
- 239000000956 alloy Substances 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims description 4
- 239000010949 copper Substances 0.000 abstract description 25
- 238000005266 casting Methods 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003723 Smelting Methods 0.000 abstract 1
- 238000007493 shaping process Methods 0.000 abstract 1
- 239000005300 metallic glass Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 230000008018 melting Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000006698 induction Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004512 die casting Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 229910000767 Tm alloy Inorganic materials 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- Conductive Materials (AREA)
Abstract
An amorphous Zr-based alloy with high shaping power contains Al (5-12 atom%), Cu (15-37), Ni (5-20), Y (2-17) and Zr (48-65). It can be shaped by casting with copper mould. It has lower smelting point and crystallizing temp.
Description
The present invention relates to a kind of composition proportion scope, preparation technology of zirconium-base amorphous alloy of high formation ability.
The composition of inquiring into the amorphous bulk of big formation ability is the focus of current non-crystalline material research.Make up than different elements with atomic radius according to the mixture heat between alloy phase diagram, element, investigate its amorphous formation ability, thereby design bulk amorphous alloy with higher formation ability.Bulk amorphous alloy is because its constructional feature and superior performance, as high yield strength, elastic limit and good anti-corrosion capability and higher fracture toughness property, therefore (W.L.Johnson all is significant on its research is still used theoretically, Bulk Glass-Forming Metallic Alloys:Science andTechnology, MRS BULLETIN, OCTOBER 1999, P42~P56).At the nineties initial stage, the U.S., Japan successively develop Zr-Ti-TM and Zr-Al-TM (TM is a transition metal) bulk amorphous alloys, and are applied at aspect such as military, civilian.Polynary bulk amorphous alloy basic technical features is to have higher reduction glass transformation temperature T
RgOr T
Xg(glass transformation temperature T
gOr crystallization temperature T
xWith liquidus temperature T
LRatio) (A.Inoue, T.Zhang, W.Zhang and A.Takeuchi, Bulk Nd-Fe-Al Amorphous Alloys With Hard Magnetic Properties, MaterialsTransaction, JIM, 37 (1996) 99-108).T
gBe subjected to the influence of composition of alloy less, and T
LBe subjected to the influence of composition bigger, near the alloy the therefore dark eutectic point is owing to have higher T
RgAnd form amorphous easily.Nearest research has further proved this viewpoint (G.J.FAN, W.LOSER, S.ROTHand J.ECHERT, Glass-Forming Ability of RE-Al-TM Alloys (Re=Sm, Y; TM=Fe, Co, Cu.Acta mater, 48 (2000) 3823-3831).
The invention provides a kind of zirconium-base amorphous alloy of high formation ability, it is characterized in that alloy is by following element and unavoidable impurities composed atom per-cent:
Al 5~12%
Cu 15~37%
Ni 5~20%
Y 2~17%
Zr 48~65%。
Can also contain Ti 0.1~15% atom in the alloy of the present invention; Impurity element oxygen preferably defines and is O
2<500ppm.
The present invention designs by composition, makes zirconium-base amorphous eutectic point reduce greatly, adopts ordinary copper die cast method can form the amorphous bulk of cm magnitude.
Mother alloy of the present invention can adopt arc melting also can adopt induction melting.Reflow process during preparation generally adopts induction melting.The preparation method can adopt and get rid of band, common copper mold casting, suction casting (suction casting), die casting (die casting), jet moulding (spray casting.) and water quenching (water quenching) prepares.Get rid of band and be suitable for the little composition of amorphous formation ability, other method is suitable for the big amorphous component of formation ability.The vacuum tightness of equipment is not less than 8 * 10 in the preparation process
-3Pa, argon shield pressure are 300~500mbar.
The present invention has following advantage:
1, certain composition proportion can form amorphous bulk.
2, do not contain poisonous element beryllium.
3, formation ability is not less than existing zirconium-base amorphous alloy.
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
1 adopts purity greater than 99.9% raw metal, adopts the arc melting mother alloy, adopts induction heating copper mold castmethod cast Zr then
56.5Cu
19Al
8.5Ni
8Ti
4Y
4Non-crystaline amorphous metal, T
1Be 748K, T
xBe 650K, can be made into the amorphous bulk of φ 6 * 70.
Embodiment 2
Adopt purity greater than 99.9% raw material, adopt the arc melting mother alloy, utilize induction heating cast Zr then
54.5Cu
19Al
8.5Ni
8Ti
4Y
6Non-crystaline amorphous metal, T
1Be 730K, T
xBe 640K, can be made into the amorphous bulk of φ 8 * 70.
Embodiment 3
Adopt purity greater than 99.9 raw material, adopt the arc melting mother alloy, utilize induction heating cast Zr then
42Cu
27Ni
10Ti
5Y
15Non-crystaline amorphous metal can be made into the amorphous bulk of φ 3 * 50.
Embodiment 4
Adopt purity greater than 99.9 raw material, adopt the arc melting mother alloy, utilize induction heating cast Zr then
54Cu
25Ni
8Y
13Non-crystaline amorphous metal can be made into the amorphous bulk of φ 3 * 50.
Comparative example 1
Zr
41.2Ti
13.8Cu
12.5Ni
10Be
22.5Non-crystaline amorphous metal liquidus line T
1(top temperature) is 937K, T
xAbout 740K (Y.J.Kim, R.Busch, and W.L.Johnson, Metallic Glass Formation inHighly Undercooled Zr
41.2Ti
13.8Cu
12.5Ni
10Be
22.5During Containerless ElectrostaticLevitation Processing, Appl.Phys.Lett.65 (1994) 2136-2138), and embodiment 2 alloy Zr
54.5Cu
19Al
8.5Ni
8Ti
4Y
6T
1Be 730K, T
xBe 640K.As seen fusing point reduces 200K, and crystallization temperature point T
xOnly reduce 100K:
Comparative example 2
Zr
65A
17.5Ni
10Cu
17.5Bulk amorphous alloy liquidus line (top temperature) is about 1150K, T
xAbout 750K (A.Inoue, T.Zhang, N.Nishiyama, K.ohba and T.Masumoto, Preparation of16mm Diameter Rod of Amorphous Zr
65Al
7.5Ni
10Cu
17.5Alloy, MaterialsTransaction, JIM, 34 (1993), 1234-1237.).And embodiment 1 non-crystaline amorphous metal Zr
56.5Cu
19Al
8.5Ni
8Ti
4Y
4T
1Be 748K, T
xBe 650K.As seen fusing point reduces 400K, and crystallization temperature point T
xOnly reduce 100K.The copper mould casting that two kinds of alloys carry out under the same terms is tested Zr
56.5Cu
19Al
8.5Ni
8Ti
4Y
4Be easy to form the complete non-crystal bar that diameter is 3mm, and Zr
65Al
17.5Ni
10Cu
17.5Then can not form whole amorphous.
Comparative example 3
Zr
55Al
10Ni
5Cu
30The liquidus temperature T of non-crystaline amorphous metal
1(top temperature) is 1115K through the DTA actual measurement.T
xAbout 767K (A.Inoue and T.Zhang, Fabrication of Bulk GlassyZr
55Al
10Ni
5Cu
30Alloy of 30mm in Diameter by a Suction Casting Method, Materials Transaction, JIM, 37 (1996), 185-187.).And embodiment 1 non-crystaline amorphous metal Zr
56.5Cu
19Al
8.5Ni
8Ti
4Y
4T
1Be 748K, T
xBe 650K.As seen fusing point reduces 367K, and crystallization temperature point T
xOnly reduce 117K.The copper mould casting that two kinds of alloys carry out under the same terms is tested Zr
56.5Cu
19Al
8.5Ni
8Ti
4Y
4Can obtain diameter is the complete non-crystal bar of 6mm, and Zr
55Al
10Ni
5Cu
30Then there is the part crystalline state to exist mutually.
Claims (3)
1, a kind of zirconium-base amorphous alloy of high formation ability is characterized in that alloy is by following element and unavoidable impurities composed atom per-cent:
Al 5~12%
Cu 15~37%
Ni 5~20%
Y 2~17%
Zr 48~65%。
2, by the zirconium-base amorphous alloy of the described high formation ability of claim 1, it is characterized in that: contain Ti 0.1~15% atom in the alloy.
3, by the zirconium-base amorphous alloy of claim 1 or 2 described high formation abilities, it is characterized in that: impurity element O
2<500ppm.
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CN 00123186 CN1131336C (en) | 2000-11-01 | 2000-11-01 | Zr-based amorphous alloy with high formation power |
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CN 00123186 CN1131336C (en) | 2000-11-01 | 2000-11-01 | Zr-based amorphous alloy with high formation power |
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Publication Number | Publication Date |
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CN1351192A true CN1351192A (en) | 2002-05-29 |
CN1131336C CN1131336C (en) | 2003-12-17 |
Family
ID=4589658
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Cited By (20)
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WO2007004991A1 (en) * | 2005-06-30 | 2007-01-11 | National University Of Singapore | Alloys, bulk metallic glass, and methods of forming the same |
CN1308096C (en) * | 2004-04-12 | 2007-04-04 | 北京有色金属研究总院 | Method for processing lump non-crystal alloy blank and its device used thereof |
CN100424215C (en) * | 2007-02-09 | 2008-10-08 | 华中科技大学 | Non-nickel and non-copper zirconium-based bulk amorphous alloy |
CN100432272C (en) * | 2005-12-28 | 2008-11-12 | 中国科学院金属研究所 | Zirconium base massive nano-amorphous alloy with larger plastic strain |
CN100447287C (en) * | 2007-02-01 | 2008-12-31 | 北京航空航天大学 | New type zirconium-based amorphous alloy |
CN102021502A (en) * | 2010-12-15 | 2011-04-20 | 江苏大学 | Method for preparing large-size bulk amorphous alloy |
WO2011050680A1 (en) * | 2009-10-26 | 2011-05-05 | Byd Company Limited | Zr-BASED AMORPHOUS ALLOY AND PREPARING METHOD THEREOF |
CN102517525A (en) * | 2011-12-31 | 2012-06-27 | 北京航空航天大学 | Copper mould casting and ironing combined method for preparing corrosion-resistant Zr-based amorphous alloy |
WO2013087040A1 (en) * | 2011-12-15 | 2013-06-20 | Shenzhen Byd Auto R&D Company Limited | Method of manufacturing amorphous alloy article |
CN103484800A (en) * | 2013-09-10 | 2014-01-01 | 黄利敏 | Zirconium-based amorphous alloy and preparation method thereof |
WO2014079188A1 (en) * | 2012-11-26 | 2014-05-30 | 华为技术有限公司 | Zirconium-based amorphous alloy |
CN103938132A (en) * | 2013-08-22 | 2014-07-23 | 中国科学院金属研究所 | Zr-based amorphous alloy having strong glass-forming ability |
CN104894404A (en) * | 2015-03-19 | 2015-09-09 | 中信戴卡股份有限公司 | Aluminum alloy refiner, and preparation method and application thereof |
US9745652B2 (en) | 2012-11-26 | 2017-08-29 | Huawei Technologies Co., Ltd. | ZR-based amorphous alloy |
CN108220701A (en) * | 2018-01-17 | 2018-06-29 | 昆明理工大学 | A kind of non-crystalline grains reinforced aluminium-base composite material and preparation method thereof |
CN109468548A (en) * | 2019-01-04 | 2019-03-15 | 盘星新型合金材料(常州)有限公司 | A kind of width supercooling liquid phase region zirconium-base amorphous alloy |
CN110331349A (en) * | 2019-07-10 | 2019-10-15 | 中国科学院金属研究所 | A kind of method of smelting of zirconium-base amorphous alloy master alloy |
CN107058913B (en) * | 2017-04-11 | 2020-04-07 | 中国科学院金属研究所 | Zirconium-based amorphous alloy with high zirconium content and preparation method thereof |
CN112391587A (en) * | 2020-10-09 | 2021-02-23 | 太原理工大学 | Preparation method and application of amorphous alloy material toughened in cryogenic cycle combined pre-deformation mode |
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-
2000
- 2000-11-01 CN CN 00123186 patent/CN1131336C/en not_active Expired - Fee Related
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CN1308096C (en) * | 2004-04-12 | 2007-04-04 | 北京有色金属研究总院 | Method for processing lump non-crystal alloy blank and its device used thereof |
WO2007004991A1 (en) * | 2005-06-30 | 2007-01-11 | National University Of Singapore | Alloys, bulk metallic glass, and methods of forming the same |
GB2441330A (en) * | 2005-06-30 | 2008-03-05 | Univ Singapore | Alloys, bulk metallic glass, and methods of forming the same |
US9290829B2 (en) | 2005-06-30 | 2016-03-22 | National University Of Singapore | Alloys, bulk metallic glass, and methods of forming the same |
GB2441330B (en) * | 2005-06-30 | 2011-02-09 | Univ Singapore | Alloys, bulk metallic glass, and methods of forming the same |
CN101297053B (en) * | 2005-06-30 | 2011-02-23 | 新加坡国立大学 | Alloys, bulk metallic glass, and methods of forming the same |
CN100432272C (en) * | 2005-12-28 | 2008-11-12 | 中国科学院金属研究所 | Zirconium base massive nano-amorphous alloy with larger plastic strain |
CN100447287C (en) * | 2007-02-01 | 2008-12-31 | 北京航空航天大学 | New type zirconium-based amorphous alloy |
CN100424215C (en) * | 2007-02-09 | 2008-10-08 | 华中科技大学 | Non-nickel and non-copper zirconium-based bulk amorphous alloy |
WO2011050680A1 (en) * | 2009-10-26 | 2011-05-05 | Byd Company Limited | Zr-BASED AMORPHOUS ALLOY AND PREPARING METHOD THEREOF |
CN102021502A (en) * | 2010-12-15 | 2011-04-20 | 江苏大学 | Method for preparing large-size bulk amorphous alloy |
WO2013087040A1 (en) * | 2011-12-15 | 2013-06-20 | Shenzhen Byd Auto R&D Company Limited | Method of manufacturing amorphous alloy article |
CN102517525A (en) * | 2011-12-31 | 2012-06-27 | 北京航空航天大学 | Copper mould casting and ironing combined method for preparing corrosion-resistant Zr-based amorphous alloy |
US9745652B2 (en) | 2012-11-26 | 2017-08-29 | Huawei Technologies Co., Ltd. | ZR-based amorphous alloy |
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CN103938132A (en) * | 2013-08-22 | 2014-07-23 | 中国科学院金属研究所 | Zr-based amorphous alloy having strong glass-forming ability |
CN103484800B (en) * | 2013-09-10 | 2015-12-09 | 黄利敏 | A kind of zirconium-base amorphous alloy and preparation method thereof |
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