CN108504963B - La-based amorphous alloy with excellent amorphous forming ability and preparation method thereof - Google Patents

La-based amorphous alloy with excellent amorphous forming ability and preparation method thereof Download PDF

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CN108504963B
CN108504963B CN201710102188.4A CN201710102188A CN108504963B CN 108504963 B CN108504963 B CN 108504963B CN 201710102188 A CN201710102188 A CN 201710102188A CN 108504963 B CN108504963 B CN 108504963B
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amorphous alloy
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amorphous
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CN108504963A (en
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王寅霄
李毅
姚佳昊
潘杰
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Institute of Metal Research of CAS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • 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

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Abstract

The invention discloses a La-based amorphous alloy with excellent amorphous forming ability and a preparation method thereof, and is characterized in that the La-based amorphous alloy comprises the following components: laaCobAlcAnd a, b and c are atomic percent, wherein: a is more than or equal to 60 and less than or equal to 80, b is more than or equal to 10 and less than or equal to 30, c is more than or equal to 10 and less than or equal to 30, and a + b + c is equal to 100. The La-based amorphous alloy provided by the invention can be prepared from industrial raw materials, has good amorphous forming capability and excellent comprehensive performance, has low requirement on vacuum degree in the preparation process, is easy to realize industrial production, and has wide application prospect.

Description

La-based amorphous alloy with excellent amorphous forming ability and preparation method thereof
Technical Field
The invention relates to amorphous alloy, and particularly provides La-based amorphous alloy and a preparation method thereof.
Background
The massive amorphous alloy becomes a research hotspot due to the excellent comprehensive performance and wide application prospect, but how to prepare the large-size amorphous alloy is still a main problem in industrial application. When the liquid alloy is cooled, atoms tend to be regularly arranged, the atoms can be ensured to keep a long-range disordered state only at a sufficiently high cooling speed, and the cooling speed is reduced when the size is too large, so that the amorphous alloy is difficult to form. The rare earth-based bulk amorphous alloy has good amorphous forming capability, and the preparation process is insensitive to oxygen and the process conditions are not harsh. Meanwhile, the rare earth based amorphous alloy has excellent comprehensive properties, such as lower melting point, wider supercooling liquid interval, special hard magnetic property, superplasticity, thermoplasticity, relatively high strength and ductility and the like. Therefore, the rare earth based amorphous alloy has great potential in industrial application.
China has rich rare earth metal resources, and the content of La in rare earth elements is second to that of cerium. A lot of reports have been made on the research of La-based bulk amorphous alloy, and the La-Cu-Ni-Al quaternary amorphous alloy obtained by adopting a copper die casting method has the maximum diameter of 12mm and the component of La55Al25Ni10Cu5Co5The size of the amorphous alloy is 9mm at most. The Babyon et al also prepared bulk La-based amorphous alloy (amorphous alloy coating with diameter of 12mm and thickness of 5 mm) by spray deposition forming, but due to the characteristics of the technique and the sharp increase of viscosity coefficient during amorphous solidification, the prepared amorphous alloy has the defects of molten drop boundary, porosity, holes and the like, thereby affecting the mechanical properties.
The invention provides a molecular formula LaaCobAlcThe amorphous alloy and the preparation method thereof, wherein a, b and c are atomic percent. The amorphous alloy is only a ternary alloy system, but has very good amorphous forming capability and excellent comprehensive performance. More importantly, the amorphous alloy can be prepared from low-cost industrial raw materials and has a relatively simple preparation process. Therefore, the La-based amorphous alloy has a very wide prospect in large-scale industrial application.
Disclosure of Invention
The invention provides an La-based amorphous alloy and a preparation method thereof, which have the advantages that: on one hand, the amorphous alloy adopts metal with industrial grade purity, and the cost is lower; on the other hand, the amorphous alloy has good forming capability, is insensitive to oxygen content in the preparation process, and has good industrial application prospect.
An La-based amorphous alloy, the composition of which is: laaCobAlcAnd a, b and c are atomic percent, wherein: a is more than or equal to 60 and less than or equal to 80, b is more than or equal to 10 and less than or equal to 30, and c is more than or equal to 10 and less than or equal to 30. When the La-based amorphous alloy is cast into a rod-shaped sample with the diameter of more than or equal to 8mm and the length of 60mm, the amorphous content is 30-99 percent based on the total volume of the alloy.
The La-based amorphous alloy is characterized in that: a. the preferable value ranges of b and c (atomic percent) are as follows: a is more than or equal to 66 and less than or equal to 76, b is more than or equal to 12 and less than or equal to 22, and c is more than or equal to 12 and less than or equal to 22. When the La-based amorphous alloy is cast into a rod-shaped sample with the diameter of more than or equal to 12mm and the length of 60mm, the amorphous content is more than 50 percent based on the total volume of the alloy.
The invention also provides a preparation method of the La-based amorphous alloy, which is characterized by comprising the following steps: firstly, weighing each component according to the atomic percentage of the amorphous alloy for configuration; then, preparing a master alloy ingot with required components by an arc melting method under the protective gas atmosphere, wherein the melting temperature of the alloy is more than 2000 ℃, the melting time is more than 30 seconds, and the alloy is repeatedly melted for at least 6 times; and finally, obtaining the amorphous alloy by a copper mold casting method.
The preparation method of the La-based amorphous alloy is characterized by comprising the following steps: the purity of the raw materials for preparing the amorphous alloy is more than 97 percent, and industrial-grade metal La is adopted; in addition, the amorphous alloy is easy to manufacture, the requirement on vacuum condition is not high, the vacuum degree is kept to be 0.1-1000 Pa under general conditions, smelting protective gas is inert gas, the alloy is cooled to be amorphous after smelting, and the cooling speed is preferably higher than 10K/s. Under the condition of simultaneously meeting the requirements of low cost and low vacuum degree, the amorphous alloy still has good forming capability and mechanical property, is easy to realize industrial production and has wide application prospect.
Detailed Description
The following examples used starting materials with a purity of > 97% and argon with a purity of > 97%.
Example 1
The components: la68Co17Al15
Weighing the raw materials according to the atomic percentage of the components, preparing, and vacuumizing to 0.1 Pa; then smelting the raw materials in an argon atmosphere at the smelting temperature of 2000 ℃, and repeatedly smelting for 6 times; finally, the melt was cast into a mold to obtain a rod-like sample of phi 14 x 60mm in size with an amorphous percentage of 95% by volume.
Example 2
The components: la66Co12Al22
Weighing the raw materials according to the atomic percentage of the components, preparing, and vacuumizing to 5 Pa; then smelting the raw materials in an argon atmosphere at the smelting temperature of 2000 ℃, and repeatedly smelting for 6 times; finally, the melt was cast into a mold to obtain a rod-like sample of 12X 60mm in size phi with 90% amorphous content by volume.
Example 3
The components: la60Co10Al30
Weighing the raw materials according to the atomic percentage of the components, preparing, and vacuumizing to 0.1 Pa; then smelting the raw materials in an argon atmosphere at the smelting temperature of 2000 ℃, and repeatedly smelting for 8 times; finally, the melt was cast into a mold to obtain a rod-like sample of 8 x 60mm size with 40% amorphous by volume.
Example 4
The components: la80Co10Al10
Weighing the raw materials according to the atomic percentage of the components, preparing, and vacuumizing to 5 Pa; then smelting the raw materials in an argon atmosphere at the smelting temperature of 2000 ℃, and repeatedly smelting for 6 times; finally, the melt was cast into a mold to obtain a rod-like sample of phi 10 x 60mm in size with an amorphous percentage by volume of 70%.
Example 5
The components: la66Co22Al12
Weighing the raw materials according to the atomic percentage of the components, preparing, and vacuumizing to 0.1 Pa; then smelting the raw materials in an argon atmosphere at the smelting temperature of 2000 ℃, and repeatedly smelting for 8 times; finally, the melt was cast into a mold to obtain a rod-like sample of phi 12 x 60mm in size with 80% amorphous by volume.
Example 6
The components: la76Co12Al12
Weighing the raw materials according to the atomic percentage of the components, preparing, and vacuumizing to 0.1 Pa; then smelting the raw materials in an argon atmosphere at 2200 ℃ for 8 times; finally, the melt was cast into a mold to obtain a rod-like sample of 12X 60mm in size phi with 90% amorphous content by volume.
Example 7
The components: la60Co30Al10
Weighing the raw materials according to the atomic percentage of the components, preparing, and vacuumizing to 0.1 Pa; then smelting the raw materials in an argon atmosphere at the smelting temperature of 2000 ℃, and repeatedly smelting for 8 times; finally, the melt was cast into a mold to obtain a rod-like sample of phi 8 x 60mm in size with an amorphous percentage of 50% by volume.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (5)

1. An La-based amorphous alloy characterized by: the La-based amorphous alloy consists of LaaCobAlcAnd a, b and c are atomic percent, wherein: a. the value ranges of b and c are as follows: a is more than or equal to 66 and less than or equal to 76, b is more than or equal to 12 and less than or equal to 22, c is more than or equal to 12 and less than or equal to 22, and a + b + c is equal to 100;
the preparation method of the La-based amorphous alloy comprises the following steps of firstly, weighing each component according to the atomic percentage of the amorphous alloy for configuration; then, preparing a master alloy ingot with required components by an arc melting method under the protective gas atmosphere, wherein the melting temperature of the alloy is more than 2000 ℃, the melting time is more than 30 seconds, and the alloy is repeatedly melted for at least 6 times; finally, obtaining the amorphous alloy sample by a copper mold casting method; in the alloy composition area, the diameter of the amorphous alloy bar obtained by adopting a copper die casting method is more than or equal to 12 mm; the alloy is smelted under the vacuum condition, and the required vacuum degree is 0.1-1000 Pa.
2. A method for preparing the La-based amorphous alloy according to claim 1, characterized in that: firstly, weighing each component according to the atomic percentage of the amorphous alloy for configuration; then, preparing a master alloy ingot with required components by an arc melting method under the protective gas atmosphere, wherein the melting temperature of the alloy is more than 2000 ℃, the melting time is more than 30 seconds, and the alloy is repeatedly melted for at least 6 times; finally, obtaining the amorphous alloy sample by a copper mold casting method; in the alloy composition area, the diameter of the amorphous alloy bar obtained by adopting a copper die casting method is more than or equal to 12 mm; the alloy is smelted under the vacuum condition, and the required vacuum degree is 0.1-1000 Pa.
3. The method for preparing an amorphous alloy according to claim 2, wherein: the purity of the raw materials for preparing the amorphous alloy is more than 97 percent.
4. The method for preparing an amorphous alloy according to claim 2, wherein: the smelting protective gas is inert gas.
5. The method for preparing an amorphous alloy according to claim 2, wherein: and after the alloy is smelted, cooling the alloy to an amorphous state, wherein the cooling speed is more than 10K/s.
CN201710102188.4A 2017-02-24 2017-02-24 La-based amorphous alloy with excellent amorphous forming ability and preparation method thereof Active CN108504963B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0387338A (en) * 1989-08-31 1991-04-12 Takeshi Masumoto Rare earth metal-base alloy foil or rare earth metal-base alloy fine wire and its manufacture
CN1936058A (en) * 2006-09-30 2007-03-28 北京航空航天大学 La-Ce base amorphous alloy
CN1952201A (en) * 2005-10-21 2007-04-25 中国科学院物理研究所 Mixed rare earths-based amorphous metal plastic

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0387338A (en) * 1989-08-31 1991-04-12 Takeshi Masumoto Rare earth metal-base alloy foil or rare earth metal-base alloy fine wire and its manufacture
CN1952201A (en) * 2005-10-21 2007-04-25 中国科学院物理研究所 Mixed rare earths-based amorphous metal plastic
CN1936058A (en) * 2006-09-30 2007-03-28 北京航空航天大学 La-Ce base amorphous alloy

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
Effect of similar elements on improving glass-forming ability of La–Ce-based alloys;Tao Zhang等;《Journal of Alloys and Compounds》;20081117;第483卷;表1 *
Formation and mechanical properties of (Ce–La–Pr–Nd)–Co–Al bulk glassy alloys with superior glass-forming ability;Ran Li等;《Scripta Materialia》;20051228;第54卷;摘要 *
Glass forming ability and thermodynamic properties in novel La-Al-Cu-Co bulk metallic glasses;LI Peiyou等;《JOURNAL OF RARE EARTHS》;20150930;第33卷(第9期);表1 *
Influence of similar atom substitution on glass formation in (La–Ce)–Al–Co bulk metallic glasses;Ran Li等;《Acta Materialia》;20070405;第55卷;表2 *
Ternary La-Al-C bulk metallic glasses;Leilei Zhang等;《Intermetallics》;20140419;第52卷;第92页左栏第2段 *
The Influence of Similar Element Coexistence in (La-Ce)-Al-(Co-Cu) Bulk Metallic Glasses;Ran Li等;《Materials Transactions》;20070620;第48卷(第7期);第1681页左栏第1段 *

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