CN100357480C - La base bulk amorphous alloy - Google Patents

La base bulk amorphous alloy Download PDF

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Publication number
CN100357480C
CN100357480C CNB2006100516650A CN200610051665A CN100357480C CN 100357480 C CN100357480 C CN 100357480C CN B2006100516650 A CNB2006100516650 A CN B2006100516650A CN 200610051665 A CN200610051665 A CN 200610051665A CN 100357480 C CN100357480 C CN 100357480C
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alloy
amorphous
amorphous alloy
purity
series
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CN1851031A (en
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蒋建中
姜清奎
张国庆
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The present invention discloses a La base bulk amorphous alloy. The series bulk amorphous alloy comprises amorphous phases with the volume fraction of 50 to 100%, and the structural formula of the series alloy is LaxAl14(Cu<5/6>Ag<1/6>)<76-x>Ni5Co5, wherein x is the atomic percentage of La elements, and x is more than or equal to 60 and at most 68. The series bulk amorphous alloy has the following advantages: (1)the dimension of the alloy is large, and the diameter of a complete amorphous alloy rod reaches at least 20mm; (2)The alloy has a glass transition temperature of less than 150 DEG C; (3)The thermal stability of the alloy is good, and the alloy has a wide supercooled liquid region whose temperature can reach 43 to 73 DEG C. The series amorphous alloy has an excellent property, and thus, the alloy has a wide application prospect, and the alloy is a new material used in the fields of micromachines, micro nano imprints, etc.

Description

The La base large amorphous alloy
Technical field
The present invention relates to the amorphous alloy field, particularly the La base large amorphous alloy.
Background technology
Amorphous alloy is that the composed atom arrangement is not periodically and a symmetric class novel alloy material.Because its special microtexture causes them to have superior mechanics, physics, chemistry and magnetic property, as high strength, high rigidity, wear-resistant, corrosion-resistant.These superior performances make amorphous alloy have application potential in a lot of fields.
Simultaneously, amorphous alloy also has the weakness of self, has limited its application.The main difficulty that amorphous alloy faces in using is: 1) prepare large-sized amorphous alloy.Metal and alloy liquid tend to be transformed into the crystalline material that atomic rule is arranged in process of cooling, seek out the amorphous alloy of atom long-range lack of alignment, and it is enough fast that speed of cooling is wanted, make atom also have little time to be arranged in crystalline structure with regard to frozen firmly.Under the identical situation of other conditions, along with the big increase of sample size, speed of cooling slows down, and causes large-sized amorphous alloy to be difficult to obtain.2) raising of thermostability.Amorphous alloy is in the thermodynamics metastable state, the trend that oriented thermodynamics stable state-crystalline state changes, and this transition temperature is called crystallization temperature.Therefore in order in bigger temperature range, to use amorphous material, just need to improve the thermostability of amorphous alloy, the high alloy system of exploitation thermostability.3) reduction of amorphous alloy glass transformation temperature.Common amorphous metal has superplastic behavior between second-order transition temperature and crystallization temperature, but very high glass transformation temperature makes the superplasticity property of this excellence of amorphous metal obtain considerable restraint in industrial application, and the second-order transition temperature that how to reduce metallic glass is to develop it at the superplasticity property of supercooling liquid phase region with can impress the focus that performance becomes present amorphous alloy area research.
Summary of the invention
The objective of the invention is to develop have high glass forming ability, thermostability height, a kind of La base large amorphous alloy (non-crystaline amorphous metal that size reaches millimeter magnitude is called as bulk amorphous alloys) that second-order transition temperature is low.
The technical solution adopted for the present invention to solve the technical problems is as follows:
1.La base large amorphous alloy, this Al-Cu-Zn block amorphous alloy comprises the amorphous phase of volume fraction 50～100%, and this is that the structural formula of alloy is La xAl 14(Cu 5/6Ag 1/6) 76-xNi 5Co 5, wherein x is a La atoms of elements percentage ratio, 60≤x≤68.
2.La the component La of base large amorphous alloy, Al, Cu, Ag, Ni, the material purity of Co are 96%～99.95%.
The beneficial effect that the present invention has is: this Al-Cu-Zn block amorphous alloy has following advantage: 1) size is big, and the diameter of amorphous alloy rod reaches 20mm at least fully; 2) has glass transformation temperature less than 150 ℃; 3) Heat stability is good has the wide supercooling liquid phase region that reaches 43～73 ℃.Therefore, this alloy has broad application prospects in fields such as micromechanics, micro-nano imprint materials.
Description of drawings
Fig. 1 is the XRD figure according to the La base large amorphous alloy of embodiment 1-5 preparation;
Fig. 2 is the DSC figure according to the La base large amorphous alloy of embodiment 1-5 preparation;
Fig. 3 is the stress-strain curves according to the La base large amorphous alloy of embodiment 1 preparation.
Embodiment
Step 1: melting La in the vacuum melting furnace of argon shield xAl 14(Cu 5/6Ag 1/6) 76-xNi 5Co 5, wherein x is a La atoms of elements percentage ratio, 60≤x≤68.At least melt back is four times, to guarantee the even of alloy pig subconstiuent.
Step 2: adopt suction casting method that the alloy spindle that step 1 obtains is prepared into the bulk amorphous alloys sample.
Step 3: characterize the gained structures of samples with the x ray diffraction method, obtain thermodynamical coordinate with dsc, and according to material generation crystallization liberated heat, be the percent by volume of recently weighing amorphous alloy of area with the complete non-crystalline state sample exothermic peak area of exothermic peak in the differential thermal analysis curve, as La 68Al 14(Cu 5/6Ag 1/6) 8Ni 5Co 5The amorphous heat release be 21.3J/g, and its complete non-crystalline state sample heat release is 28.6J/g, the volume fraction of its amorphous of drum is 75%.With mechanics performance test machine, the mechanical property of specimen.
Embodiment 1:
It is that 20mm, amorphous volume content are 100% La that this embodiment adopts suction casting method to prepare diameter 62Al 14(Cu 5/6Ag 1/6) 14Ni 5Co 5Bulk amorphous alloys.
Step 1: with purity is that 99.6% La, purity are that 99.5% Al, purity are that 99.95% Cu, purity are that 99.8% Ag, purity are that 99.8% Ni and purity are that 99.9% Co is by La 62Al 14(Cu 5/6Ag 1/6) 14Ni 5Co 5Proportioning is arc melting in the argon atmospher of zirconium absorption, obtains the alloy spindle that mixes.
Step 2: melting on the water cooled copper mould of spindle in the smelting furnace of argon shield of step 1 acquisition.
Step 3: utilize pressure difference that step 2 is obtained the water cooled copper mould that alloy liquid injects internal diameter 20mm.Make bulk amorphous alloys.
Step 4: characterize this large block amorphous structure with the x ray diffraction method, Fig. 1 is the x x ray diffration pattern x of this sample.
Step 5: the thermodynamical coordinate that obtains this bulk sample with dsc.The DSC curve is shown in Fig. 2.
Step 6: the mechanical property of employing testing machine for mechanical properties test gained material as shown in Figure 3.
By Fig. 1 and Fig. 2 as can be known this embodiment obtained the bulk amorphous alloys of diameter 20mm.The performance of the bulk amorphous alloys that this embodiment obtains is as shown in table 1.
Table 1La 62Al 14(Cu 5/6Ag 1/6) 14Ni 5Co 5The performance of bulk amorphous alloys
Composition (at.%) Glass transformation temperature T g(K) Crystallization temperature T x(K) Surpass cold liquid zone Δ T x(K) Compressed rupture strength σ (MPa)
La 62Al 14(Cu 5/6Ag 1/6) 14Ni 5Co 5 418 491 73 650
Embodiment 2:
It is that 20mm, amorphous volume content are 100% La that this embodiment adopts suction casting method to prepare diameter 64Al 14(Cu 5/6Ag 1/6) 12Ni 5Co 5Bulk amorphous alloys.
Step 1: with purity is that 99.6% La, purity are that 99.5% Al, purity are that 99.95% Cu, purity are that 99.8% Ag, purity are that 99.8% Ni and purity are that 99.9% Co is by La 64Al 14(Cu 5/6Ag 1/6) 12Ni 5Co 5Proportioning is arc melting in the argon atmospher of zirconium absorption, obtains the alloy spindle that mixes.
Step 2: melting on the water cooled copper mould of spindle in the smelting furnace of argon shield of step 1 acquisition.
Step 3: utilize pressure difference that step 2 is obtained the water cooled copper mould that alloy liquid injects internal diameter 20mm.Make bulk amorphous alloys.
Step 4: characterize this large block amorphous structure with the x ray diffraction method, Fig. 1 is the x x ray diffration pattern x of this sample.
Step 5: the thermodynamical coordinate that obtains this bulk sample with dsc.The DSC curve is shown in Fig. 2.
Embodiment 3:
It is that 20mm, amorphous volume content are 100% La that this embodiment adopts suction casting method to prepare diameter 66Al 14(Cu 5/6Ag 1/6) 10Ni 5Co 5Bulk amorphous alloys.
Step 1: with purity is that 99.6% La, purity are that 99.5% Al, purity are that 99.95% Cu, purity are that 99.8% Ag, purity are that 99.8% Ni and purity are that 99.9% Co is by La 66Al 14(Cu 5/6Ag 1/6) 10Ni 5Co 5Proportioning is arc melting in the argon atmospher of zirconium absorption, obtains the alloy spindle that mixes.
Step 2: melting on the water cooled copper mould of spindle in the smelting furnace of argon shield of step l acquisition.
Step 3: utilize pressure difference that step 2 is obtained the water cooled copper mould that alloy liquid injects internal diameter 20mm.Make bulk amorphous alloys.
Step 4: characterize this large block amorphous structure with the x ray diffraction method, Fig. 1 is the x x ray diffration pattern x of this sample.
Step 5: the thermodynamical coordinate that obtains this bulk sample with dsc.The DSC curve is shown in Fig. 2.
Embodiment 4:
It is that 16mm, amorphous volume content are 75% La that this embodiment adopts suction casting method to prepare diameter 68Al 14(Cu 5/6Ag 1/6) 8Ni 5Co 5Bulk amorphous alloys.
Step 1: with purity is that 96% La, purity are that 99.5% Al, purity are that 99.95% Cu, purity are that 99.8% Ag, purity are that 99.8% Ni and purity are that 99.9% Co is by La 68Al 14(Cu 5/6Ag 1/6) 8Ni 5Co 5Proportioning is arc melting in the argon atmospher of zirconium absorption, obtains the alloy spindle that mixes.
Step 2: melting on the water cooled copper mould of spindle in the smelting furnace of argon shield of step 1 acquisition.
Step 3: utilize pressure difference that step 2 is obtained the water cooled copper mould that alloy liquid injects internal diameter 16mm.Make bulk amorphous alloys.
Step 4: characterize this large block amorphous structure with the x ray diffraction method, Fig. 1 is the x x ray diffration pattern x of this sample.
Step 5: the thermodynamical coordinate that obtains this bulk sample with dsc.The DSC curve is shown in Fig. 2.
Embodiment 5:
It is that 16mm, amorphous volume content are 50% La that this embodiment adopts suction casting method to prepare diameter 60Al 14(Cu 5/6Ag 1/6) 16Ni 5Co 5Bulk amorphous alloys.
Step 1: with purity is that 96% La, purity are that 99.5% Al, purity are that 99.95% Cu, purity are that 99.8% Ag, purity are that 99.8% Ni and purity are that 99.9% Co is by La 60Al 14(Cu 5/6Ag 1/6) 16Ni 5Co 5Proportioning is arc melting in the argon atmospher of zirconium absorption, obtains the alloy spindle that mixes.
Step 2: melting on the water cooled copper mould of spindle in the smelting furnace of argon shield of step 1 acquisition.
Step 3: utilize pressure difference that step 2 is obtained the water cooled copper mould that alloy liquid injects internal diameter 16mm.Make bulk amorphous alloys.
Step 4: characterize this large block amorphous structure with the x ray diffraction method, Fig. 1 is the x x ray diffration pattern x of this sample.
Step 5: the thermodynamical coordinate that obtains this bulk sample with dsc.The DSC curve is shown in Fig. 2.

Claims (2)

1.La base large amorphous alloy is characterized in that: this Al-Cu-Zn block amorphous alloy comprises the amorphous phase of volume fraction 50～100%, and this is that the structural formula of alloy is La xAl 14(Cu 5/6Ag 1/6) 76-xNi 5Co 5, wherein x is a La atoms of elements percentage ratio, 60≤x≤68.
2. La base large amorphous alloy according to claim 1 is characterized in that: the component La of described non-crystaline amorphous metal, and Al, Ni, Cu, Ag, the material purity of Co are 96%～99.95%.
CNB2006100516650A 2006-05-26 2006-05-26 La base bulk amorphous alloy Expired - Fee Related CN100357480C (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5448637A (en) * 1977-09-27 1979-04-17 Nippon Steel Corp Method of making amorphous metal sheet
EP0691175A1 (en) * 1994-06-09 1996-01-10 Honda Giken Kogyo Kabushiki Kaisha Article made by joining two members together, and a brazing filler metal
CN1563453A (en) * 2004-04-01 2005-01-12 桂林电子工业学院 rEXmGYnI4-zAz alloy of storing hydrogen and uncrystallized preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5448637A (en) * 1977-09-27 1979-04-17 Nippon Steel Corp Method of making amorphous metal sheet
EP0691175A1 (en) * 1994-06-09 1996-01-10 Honda Giken Kogyo Kabushiki Kaisha Article made by joining two members together, and a brazing filler metal
CN1563453A (en) * 2004-04-01 2005-01-12 桂林电子工业学院 rEXmGYnI4-zAz alloy of storing hydrogen and uncrystallized preparation method

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