CN114606452A - High-plasticity Hf-based two-phase amorphous alloy and preparation method thereof - Google Patents

High-plasticity Hf-based two-phase amorphous alloy and preparation method thereof Download PDF

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CN114606452A
CN114606452A CN202210176905.9A CN202210176905A CN114606452A CN 114606452 A CN114606452 A CN 114606452A CN 202210176905 A CN202210176905 A CN 202210176905A CN 114606452 A CN114606452 A CN 114606452A
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amorphous alloy
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CN114606452B (en
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曹峻华
蔡远飞
王军强
霍军涛
张岩
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Ningbo Institute of Material Technology and Engineering 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
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D18/00—Pressure casting; Vacuum casting
    • B22D18/06—Vacuum casting, i.e. making use of vacuum to fill the mould
    • 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

Abstract

The invention discloses a high-plasticity Hf-based amorphous alloy with an atomic percentage composition formula of HfaCubNicAldAgeWherein a is more than or equal to 30 and less than or equal to 65, b is more than or equal to 25 and less than or equal to 35, c is more than or equal to 5 and less than or equal to 25, d is more than or equal to 4 and less than or equal to 15, e is more than 0 and less than 5, and a + b + c + d + e is equal to 100, the amorphous alloy is a dual-phase amorphous structure, and the dual-phase amorphous structure is composed of an HfNiAlAg-rich amorphous alloy matrix and Cu-rich second-phase amorphous alloy particles. The alloy has high strength and high plasticity. The invention also discloses a preparation method of the high-plasticity Hf-based amorphous alloy, which comprises the following steps: preparing materials according to the atomic percentage composition formula of the high-plasticity Hf-based amorphous alloy, and uniformly smelting to prepare a master alloy; and preparing the molten master alloy into the high-plasticity Hf-based amorphous alloy by a copper mold suction casting method. The method is simple and efficient, and saves resources.

Description

High-plasticity Hf-based two-phase amorphous alloy and preparation method thereof
Technical Field
The invention belongs to the design and preparation technology of amorphous alloy materials, and particularly relates to a high-plasticity Hf-based amorphous alloy and a preparation method thereof.
Background
The Amorphous alloy (also called Metallic glass) has long-range disorder, short-range ordered atomic structure and isotropic physical characteristics, has a unique glass transition temperature point, and has the characteristics of glass, metal, solid and liquid. Amorphous materials are disordered as a whole, but atoms are also bonded together by chemical bonds, so that a certain regularity, i.e., short-range order, is observed in the limited close proximity of the atoms.
In the 60 th century of the 20 th century, amorphous alloys began to be studied by professor Duwez of the university of california, producing amorphous ribbons several tens of microns thick by means of copper wheel spinning, and were shown in our lives in this way. In 1974, Chen et al prepared amorphous alloy of Pd-Cu-Si ternary system by suction casting method, and successfully crossed the size of amorphous alloy from micron level to millimeter level. In 1982, Turnbull et al added P element into Pd-Ni system, and successfully increased the size of amorphous alloy from the previous millimeter level to centimeter level by using boron oxide fluxing method. With the lapse of time, in the 20 th century, the end of the 80 s to the early 90 s, Inoue et Al, northeast Japan university, adopt a multi-alloying method, and a series of La-Al-Ni ternary system alloys which can replace precious metal systems and have high amorphous forming capability are discovered successively, so that a road is paved for industrial production, the application of amorphous alloys is promoted, and the research of bulk amorphous alloys is rapidly developed to dozens of individual systems from original systems.
Amorphous alloy refers to alloy, also called metallic glass, in which atoms are distributed in a topological disordered manner in a three-dimensional space in a solid state and relatively stable form is maintained in a certain temperature range, and when the critical dimension of the amorphous alloy reaches a millimeter level, the amorphous alloy can be called bulk amorphous alloy, and has excellent mechanical properties such as high strength, high hardness and high elastic limit, and low plasticity or severe brittleness becomes a key problem of applying the bulk amorphous alloy to structural materials.
The Hf-based amorphous alloy has excellent mechanical properties such as high strength, high wear resistance, high corrosion resistance and the like, but has poor plasticity at room temperature and is difficult to process; the wide application of the Hf-based amorphous alloy is limited. In order to improve the plasticity of the bulk amorphous alloy, nanocrystals are generated in a heat treatment mode, so that the plasticity of the bulk amorphous alloy is improved, and a large amount of manpower and material resources are wasted.
Therefore, it is highly desirable to design an Hf-based amorphous alloy with high strength, high wear resistance, and avoiding poor plasticity.
Disclosure of Invention
The invention provides a high-plasticity Hf-based amorphous alloy which has high strength and high plasticity.
A high-plasticity Hf-base amorphous alloy with atomic percentage composition formula of HfaCubNicAldAgeWherein a is more than or equal to 30 and less than or equal to 65, b is more than or equal to 25 and less than or equal to 35, c is more than or equal to 5 and less than or equal to 25, d is more than or equal to 4 and less than or equal to 15, e is more than 0 and less than 5, and a + b + c + d + e is equal to 100, the amorphous alloy is a dual-phase amorphous structure, and the dual-phase amorphous structure is composed of an HfNiAlAg-rich amorphous alloy matrix and a Cu-rich second-phase amorphous alloy.
By adding an Ag element having a positive enthalpy of mixing with both Cu and Ni to Hf-Cu-Ni-Al, phase separation typically occurs between elements having a positive enthalpy of mixing. The Hf has larger negative enthalpy of mixing (delta H) with Ni, Al and Ag elementsHf-Al＝-39kJ/mol，ΔHHf-Ni＝-42kJ/mol，ΔHHf-Ag13kJ/mol), there is a positive enthalpy of mixing (Δ H) between the three elements Ag, Cu and NiAg-Cu＝+2kJ/mol，ΔHAg-Ni＝+15kJ/mol，ΔHCu-Ni+4 kJ/mol). Therefore, the four elements of HfNiAlAg are more easily combined to form two amorphous phases rich in HfNiAlAg and Cu. In work on free volume studies using Monte Carlo simulations, it was found that amorphous local structures can be divided into soft and hard domains. The hard regions are composed of enriched icosahedral clusters, while the soft regions contain more free volume. Structural inhomogeneities therefore make it easier to create more free volume than a homogeneous structure. The large amount of free volume distributed in a dispersion mode is beneficial to the formation, branching and interaction of multiple shear bands, so that the plasticity of the bulk amorphous alloy is improved.
The atomic proportions of elements Hf, Ni, Al and Ag in the HfNiAlAg-rich amorphous alloy matrix are respectively that a is more than or equal to 30 and less than or equal to 55, c is more than or equal to 10 and less than or equal to 20, d is more than or equal to 4 and less than or equal to 15, and e is more than 0 and less than or equal to 3.
The atomic proportion of the element Cu in the Cu-rich second-phase amorphous alloy particles is 39-70%.
The diameter of the Cu-rich second-phase amorphous alloy particles is 4-10nm, and the Cu-rich second-phase amorphous alloy particles account for 5-55% of the volume of the amorphous alloy matrix.
The atomic percentage of Cu, Ni and Ag is that b is more than or equal to 25 and less than or equal to 35, c is more than or equal to 5 and less than or equal to 15, e is more than 0 and less than or equal to 2.5, the diameter of the Cu-rich second phase amorphous alloy particles is 5-9nm, and the Cu-rich second phase amorphous alloy particles account for 15-55% of the volume percentage of the amorphous alloy matrix.
The diameter of the high-plasticity Hf-based amorphous alloy is 1-10mm, the yield strength is 2325-2450MPa, and the plastic strain is 3.0-4.3%.
The invention also provides a preparation method of the high-plasticity Hf-based amorphous alloy, which comprises the following steps:
(1) preparing materials according to the atomic percentage composition formula of the high-plasticity Hf-based amorphous alloy, and uniformly smelting to prepare a master alloy;
(2) and preparing the molten master alloy into the high-plasticity Hf-based amorphous alloy by a copper mold suction casting method.
When the copper mold suction casting method is adopted, the cooling rate of the molten alloy is 102～103k/s。
The invention adopts a copper mold suction casting method, and adds Ag element which has positive mixing enthalpy with Cu and Ni in Hf-Cu-Ni-Al under a proper cooling rate, wherein the Hf element has larger negative mixing enthalpy (delta H) with Ni, Al and Ag elementHf-Al＝-39kJ/mol，ΔHHf-Ni＝-42kJ/mol，ΔHHf-Ag13kJ/mol), there is a positive enthalpy of mixing (Δ H) between the three elements Ag, Cu and NiAg-Cu＝+2kJ/mol，ΔHAg-Ni＝+15kJ/mol，ΔHCu-Ni+4 kJ/mol). Therefore, the four elements HfNiAlAg are more easily combined, thereby forming two amorphous phases rich in HfNiAlAg and Cu.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, Ag element which has positive mixing enthalpy with Cu and Ni is introduced into Hf-based amorphous alloy to form two mutually incompatible liquid phases, and a two-phase amorphous composite material is formed after glass transition and solidification.
(2) According to the invention, the Ag-added Hf-based amorphous alloy is made to generate a two-phase alloy by a copper mold suction casting method, so that the heat treatment process is saved, the toughness-increasing effect is achieved, and the prepared Hf-based amorphous alloy has high plasticity.
Drawings
FIG. 1 is an XRD diffraction pattern of example 1 and comparative examples 1-2;
FIG. 2 is a DSC chart of example 1 and comparative examples 1-2;
FIG. 3 is a graph of compressive stress-strain curves for example 1 and comparative examples 1-2;
FIG. 4 is a TEM image of example 1 and comparative examples 1-2, wherein FIG. 4a is a TEM image of example 1, FIG. 4b is a TEM image of comparative example 1, and FIG. 4c is a TEM image of comparative example 2;
fig. 5 is TEM images of example 1 and comparative examples 1 to 2, in which fig. 5a is a STEM image of example 1, fig. 5b is a STEM image of comparative example 1, and fig. 5c is a STEM image of comparative example 2.
Detailed Description
Because of the presence of some easily oxidizable elements in the alloy system of this experiment, the experimental raw materials used, high purity Ni, high purity Al, high purity Hf and high purity Ag, were all greater than 99.95 wt.%, and high purity Cu was 99.99 wt.%. The preparation process of the alloy is as follows:
(1) raw materials are prepared. Removing oxide skin and impurities on the surface of the sample by using an ultrasonic cleaner and a grinding machine; weighing by using a high-precision electronic balance to prepare raw materials according with the chemical formula proportion, wherein the weighing precision is +/-0.05 mg in the weighing process of each raw material;
(2) and smelting a master alloy ingot. Putting the prepared raw materials into a high vacuum arc melting furnace until the vacuum degree reaches 4 multiplied by 10-3After Pa, repeatedly washing with argon gasIntroducing argon to initiate an arc on the Ti, melting the raw materials, starting electromagnetic stirring after the raw materials are completely melted, and repeatedly turning each alloy ingot for four times and smelting for five times;
(3) and (5) carrying out suction casting on the bulk amorphous. And (3) cutting the master alloy ingot smelted in the last step into small pieces, polishing to remove impurities such as oxide skin, grease and the like on the surface of the master alloy, then carrying out vacuum arc smelting again, and carrying out suction casting on molten metal by adopting a copper mold to form the bulk amorphous alloy. Since the copper mold has 102～103The cooling rate of k/s can store the long-range disorder short-range ordered atomic arrangement of the solution into a solid state, thereby preparing the bulk amorphous alloy.
The performance test method comprises the following steps:
1. and (3) carrying out phase structure test on the prepared sample by XRD, wherein the test angle is 20-80 degrees, the test speed is 4 degrees/min, and 30-60 degrees is selected for convenience of curve statistics for description.
2. An amorphous alloy having a diameter of 2mm was subjected to DSC curve test at a heating rate of 20K/min. The glass transition temperature (Tg), crystallization temperature (Tx), melting temperature (Tm), and liquidus temperature (Tl) can be observed, further determining that the sample is an amorphous alloy.
3. A sample with a height of 4mm is cut out, a compression experiment is carried out at room temperature by adopting a 100kN universal tester, and the strain rate is 1 multiplied by 10 < -4 > s-1The compressive stress-strain curves of examples 1 to 3 and comparative examples 1 to 2 were obtained.
Example 1
The amorphous alloy comprises Hf48Cu29.25Ni9.75Al12Ag1The preparation method comprises the steps of adopting high-purity Ni, high-purity Al, high-purity Hf and high-purity Ag with the purity of more than 99.95 wt.% and high-purity Cu with the purity of 99.99 wt.% as raw materials, preparing the raw materials according to the proportion of a chemical formula, putting the raw materials into a high-vacuum arc melting furnace for melting, and preparing a master alloy ingot. And cutting the master alloy ingot, smelting again, and preparing the bulk amorphous alloy by adopting a copper mold suction casting method. Wherein the prepared amorphous alloy is a bar with the diameter of 2mm or 5 mm.
As shown in fig. 1, the XRD result shows that example 1 is a pure amorphous structure and a bulk amorphous alloy having a diameter of 5mm can be prepared. As shown in fig. 2, the glass transition temperature Tg of the amorphous alloy is 780.9K, the supercooled liquid region Δ Tx is 81.5K, and the initial melting temperature Tm is 1238.7K.
As shown in FIG. 3, the yield strength of example 1 was about 2325MPa, and the plastic strain was about 4.3%. As shown in fig. 4a, the high-resolution TEM image shows that the selected-area electron diffraction in the figure all presents a single diffuse scattering ring, which proves that the whole structure of the TEM image is in an amorphous state. Example 1 has two different phase contrasts, namely two amorphous phases, wherein the darker amorphous phase is morphologically uniform, i.e., a Cu-rich second phase amorphous alloy, having a size of 5-9 nm. As shown in FIG. 5a, the second phase amorphous alloy accounts for 15.9-51.5% of the amorphous alloy matrix by volume. The two-phase separation structure can promote local atom rearrangement of the amorphous alloy, prevent multiple nucleation and propagation of the shear band, and enhance the plasticity of the amorphous alloy at the size and density.
Example 2
The procedure of example 1 was different in that the amorphous alloy component was Hf48Cu29.25Ni9.75Al12.5Ag0.5Example 2 prepared a pure amorphous structure and was able to prepare a bulk amorphous alloy with a diameter of 10 mm. The glass transition temperature Tg of the amorphous alloy is 783.0K, the supercooled liquid region Δ Tx is 78.8K, and the initial melting temperature Tm is 1239.2K.
The yield strength of the amorphous alloy prepared in example 2 is about 2400MPa, and the plastic strain is about 3.4%. The high-resolution TEM image shows that the selected region electron diffraction shows a single diffuse scattering ring, and the structure is proved to be an amorphous structure as a whole. The amorphous alloy prepared in example 2 has two different phase contrasts, namely two amorphous phases, wherein the darker amorphous phase has a uniform morphology with a size of 4-8nm, and the second phase amorphous alloy accounts for 5.7-22.8% of the volume of the amorphous alloy matrix. The two-phase separation structure can promote local atom rearrangement of the amorphous alloy, prevent multiple nucleation and propagation of the shear band, and enhance the plasticity of the amorphous alloy at the size and density.
Example 3
The amorphous alloy has the component Hf48Cu29.25Ni9.75Al10Ag2In example 3, high-purity Ni, high-purity Al, high-purity Hf, and high-purity Ag, each having a purity of more than 99.95 wt%, and high-purity Cu, each having a purity of 99.99 wt%, were used as raw materials, and the raw materials were mixed according to the formula, and placed in a high-vacuum arc melting furnace to be melted, thereby preparing a master alloy ingot. And cutting the master alloy ingot, smelting again, and preparing the bulk amorphous alloy by adopting a copper mold suction casting method. Wherein the prepared amorphous alloy is a bar with the diameter of 2mm or 5 mm.
Example 3 is a pure amorphous structure and a bulk amorphous alloy with a diameter of 5mm can be prepared. The glass transition temperature Tg of the amorphous alloy is 776.5K, the supercooled liquid region Δ Tx is 76.5K, and the initial melting temperature Tm is 1235.2K.
Example 3 had a yield strength of about 2320MPa and a plastic strain of about 3.0%. The whole structure of the material is in an amorphous structure. Example 3 has two different phase contrasts, namely two amorphous phases, and example 2 has two different phase contrasts, namely two amorphous phases, wherein the darker amorphous phase has uniform morphology with the size of 5-10nm, and the second phase amorphous alloy accounts for 10.5-41.9% of the volume of the amorphous alloy matrix.
Comparative example 1
The amorphous alloy comprises Hf48Cu29.25Ni9.75Al13The method comprises the steps of adopting high-purity Ni, high-purity Al, high-purity Hf and high-purity Ag with the purity of more than 99.95 wt% and high-purity Cu with the purity of 99.99 wt% as raw materials, preparing the raw materials according to a chemical formula proportion, putting the raw materials into a high-vacuum arc melting furnace for melting, and preparing a master alloy ingot. And cutting the master alloy ingot, smelting again, and preparing the bulk amorphous alloy by adopting a copper mold suction casting method. Wherein the prepared amorphous alloy is a bar with the diameter of 2mm or 5 mm.
As shown in fig. 1, the XRD result shows that the amorphous alloy prepared in comparative example 1 has a single pure amorphous structure. As shown in fig. 2, the glass transition temperature Tg of the amorphous alloy is 786K, the supercooled liquid region Δ Tx is 76.7K, and the initial melting temperature Tm is 1240.4K.
As shown in FIG. 3, comparative example 1 had a yield strength of about 2410MPa and a plastic strain of about 2.7%. As shown in fig. 4b, the high-resolution TEM image shows that the selected regions in the image all show a single diffuse scattering ring by electron diffraction, which proves that the whole structure of the high-resolution TEM image shows an amorphous structure. As shown in fig. 5b, the amorphous alloy of comparative example 2 is a uniform amorphous alloy short-range structure, has no contrast of apparent contrast between light and shade, i.e., has no two-phase separation structure, and has poorer plasticity compared with example 1.
Comparative example 2
The amorphous alloy component is Hf48Cu29.25Ni9.75Al8Ag5In comparative example 2, high-purity Ni, high-purity Al, high-purity Hf, and high-purity Ag, each having a purity of greater than 99.95 wt.%, and high-purity Cu, each having a purity of 99.99 wt.%, were used as raw materials, and the raw materials were prepared according to the formula ratio, and placed in a high-vacuum arc melting furnace to be melted, thereby preparing a master alloy ingot. And cutting the master alloy ingot, smelting again, and preparing the bulk amorphous alloy by adopting a copper mold suction casting method.
As shown in fig. 1, the XRD result shows that comparative example 2 is a pure amorphous structure, and a bulk amorphous alloy having a diameter of 2mm can be prepared. As shown in fig. 2, the glass transition temperature Tg of the amorphous alloy is 767.1K, the supercooled liquid region Δ Tx is 67.9K, and the initial melting temperature Tm is 1222.8K.
As shown in FIG. 3, the yield strength of the amorphous alloy obtained in comparative example 2 was about 2203MPa, and the plastic strain was about 1.05%. As shown in fig. 4c, the high-resolution TEM image shows that the selected regions in the image all show a single diffuse scattering ring by electron diffraction, which proves that the whole structure of the high-resolution TEM image shows an amorphous structure. As shown in FIG. 5c, comparative example 2 has two different phase contrasts, i.e., two amorphous phases, and the second phase amorphous alloy accounts for 3.1 to 8.7% by volume of the amorphous alloy matrix, as compared to examples 1 to 3, and the plasticity is reduced.

Claims (8)

1. The high-plasticity Hf-based two-phase amorphous alloy is characterized in that the atomic percentage composition formula is HfaCubNicAldAgeWherein a is more than or equal to 30 and less than or equal to 65, b is more than or equal to 25 and less than or equal to 35, c is more than or equal to 5 and less than or equal to 25, d is more than or equal to 4 and less than or equal to 15, e is more than 0 and less than 5, and a + b + c + d + e is equal to 100, the amorphous alloy is a dual-phase amorphous structure, and the dual-phase amorphous structure is formed by an amorphous alloy matrixAnd second phase amorphous alloy particles rich in Cu.
2. The high plasticity Hf-based amorphous alloy as recited in claim 1, wherein the atomic proportions of the elements Hf, Ni, Al and Ag in the HfNiAlAg-rich amorphous alloy matrix are 30. ltoreq. a.ltoreq.55, 10. ltoreq. c.ltoreq.20, 4. ltoreq. d.ltoreq.15 and 0. ltoreq. e.ltoreq.3, respectively.
3. The high plasticity Hf-based amorphous alloy according to claim 1, wherein the atomic proportion of the element Cu in the Cu-rich second phase amorphous alloy particles is 39-70%.
4. The high plasticity Hf based amorphous alloy as claimed in claim 1, wherein the Cu-rich second phase amorphous alloy particles have a diameter of 4-10nm and occupy 5-55% by volume of the amorphous alloy matrix.
5. The high plasticity Hf based amorphous alloy as recited in claim 1, wherein the atomic percentage of Cu, Ni and Ag is 25 ≤ b ≤ 35, 5 ≤ c ≤ 15, 0 ≤ e ≤ 2.5, the diameter of the Cu-rich second phase amorphous alloy particles is 5-9nm, and the volume percentage of the Cu-rich second phase amorphous alloy particles in the amorphous alloy matrix is 15-55%.
6. The high plasticity Hf based amorphous alloy as recited in claim 1, wherein the diameter of the high plasticity Hf based amorphous alloy is 1-10mm, the yield strength is 2325-2450MPa, and the plastic strain is 3.0-4.3%.
7. The method for preparing a high plasticity Hf based amorphous alloy according to any one of claims 1 to 6, wherein the method comprises:
(1) preparing materials according to the atomic percentage composition formula of the high-plasticity Hf-based amorphous alloy, and uniformly smelting to prepare a master alloy;
(2) and preparing the molten master alloy into the high-plasticity Hf-based amorphous alloy by a copper mold suction casting method.
8. The method for preparing a high-plasticity Hf-based amorphous alloy according to claim 7, wherein the molten mother alloy is cooled at a cooling rate of 10 in the copper mold suction casting method2～103k/s。
CN202210176905.9A 2022-02-25 2022-02-25 High-plasticity Hf-based two-phase amorphous alloy and preparation method thereof Active CN114606452B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007063634A (en) * 2005-08-31 2007-03-15 Japan Science & Technology Agency Cu-(Hf, Zr)-Ag METAL GLASS ALLOY
JP2017031504A (en) * 2015-08-03 2017-02-09 ザ・スウォッチ・グループ・リサーチ・アンド・ディベロップメント・リミテッド Nickel-free zirconium and/or hafnium-based bulk amorphous alloy
CN106756647A (en) * 2016-12-12 2017-05-31 北京科技大学 A kind of high-ductility zirconium-based bulk amorphous alloy without nickel and preparation method thereof without beryllium
CN109722559A (en) * 2019-03-14 2019-05-07 北京科技大学 A kind of copper zirconium/hafnium base noncrystal alloy of oxygen alloy and preparation method thereof
CN114058981A (en) * 2021-11-05 2022-02-18 中国科学院宁波材料技术与工程研究所 Refractory high-entropy amorphous alloy material and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007063634A (en) * 2005-08-31 2007-03-15 Japan Science & Technology Agency Cu-(Hf, Zr)-Ag METAL GLASS ALLOY
JP2017031504A (en) * 2015-08-03 2017-02-09 ザ・スウォッチ・グループ・リサーチ・アンド・ディベロップメント・リミテッド Nickel-free zirconium and/or hafnium-based bulk amorphous alloy
CN106756647A (en) * 2016-12-12 2017-05-31 北京科技大学 A kind of high-ductility zirconium-based bulk amorphous alloy without nickel and preparation method thereof without beryllium
CN109722559A (en) * 2019-03-14 2019-05-07 北京科技大学 A kind of copper zirconium/hafnium base noncrystal alloy of oxygen alloy and preparation method thereof
CN114058981A (en) * 2021-11-05 2022-02-18 中国科学院宁波材料技术与工程研究所 Refractory high-entropy amorphous alloy material and preparation method and application thereof

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