CN110205566B - Method for improving strength of phase-change Ti-based amorphous composite material by adding Al - Google Patents

Method for improving strength of phase-change Ti-based amorphous composite material by adding Al Download PDF

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CN110205566B
CN110205566B CN201910532597.7A CN201910532597A CN110205566B CN 110205566 B CN110205566 B CN 110205566B CN 201910532597 A CN201910532597 A CN 201910532597A CN 110205566 B CN110205566 B CN 110205566B
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张龙
张晋浩
张海峰
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付华萌
李宏
朱正旺
王爱民
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Institute of Metal Research of CAS
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Abstract

The invention relates to the field of Ti-based amorphous endogenetic composite materials, in particular to a method for improving the yield of Ti-based amorphous endogenetic composite materials by adding AlA method for producing yield strength of Ti-based amorphous endogenous metastable beta-Ti composite material. The alloy system is Ti-Zr-Cu-Be- (Al), and the composition range of the alloy system is changed according to the following principle: (Ti)0.474Zr0.34Cu0.06Be0.126)100‑xAlx(atomic percent), x is 0, 4, 6, 8. According to the invention, by adjusting the content of the Al element, the Al element is found to change the component distribution coefficients of other components in the beta-Ti and amorphous matrix, so that the improvement of the phase stability of the beta-Ti is realized; in addition, Al atoms themselves and other atoms readily form covalent-like bonds with higher strength. Due to the two factors, the yield strength of the phase-change Ti-based amorphous endogenetic composite material can be remarkably improved by adding Al, and the method has important value for development and application of the amorphous composite material.

Description

Method for improving strength of phase-change Ti-based amorphous composite material by adding Al
Technical Field
The invention relates to the field of Ti-based amorphous endogenetic composite materials, in particular to a method for improving the yield strength of a Ti-based amorphous endogenetic metastable beta-Ti composite material by adding Al.
Background
The amorphous alloy has excellent mechanical properties such as high strength, high hardness, large elastic limit and the like, however, the amorphous alloy generally has no room temperature tensile plasticity, which limits the practical application of the amorphous alloy as a structural material. In order to overcome the defect of the amorphous alloy, the amorphous endogenetic composite material can be obtained by separating out a crystalline phase in the solidification process of the alloy through composition design. Ti-based amorphous, endogenous β -Ti dendrite composites can generally have significant tensile plasticity, but most exhibit a work softening phenomenon. Recent studies have shown that Ti-based amorphous endogenous composites can exhibit excellent tensile work hardening capabilities if the endogenous β -Ti phase is metastable and can undergo shape-induced martensitic transformation during deformation. The Ti-based amorphous endogenetic composite material with the deformation-induced phase change characteristic is one of hot spots of research in the field of the current amorphous composite materials.
In recent years, various researchers in China carry out a great deal of research on amorphous composite materials, and a series of Ti-based amorphous endogenous composite materials with endogenous metastable beta-Ti are prepared, wherein common systems comprise Ti-Zr-Cu-Be, Ti-Zr-Cu-Fe-Be, Ti-Zr-Cu-Co-Be, Ti-Zr-Cu-Ni-Be and the like. However, in the deformation process of the alloys, because the beta phase undergoes martensite transformation under relatively low stress, the yield strength of the amorphous composite material is very low, even the yield strength of the amorphous composite material is lower than half of that of a single-phase Ti-based amorphous alloy, which greatly limits the practical application of the phase-change Ti-based amorphous composite material, and how to improve the yield strength of the phase-change Ti-based amorphous composite material has very important technical and application values.
Disclosure of Invention
The invention aims to provide a method for improving the strength of a phase-change Ti-based amorphous composite material by adding Al, which obviously improves the tensile yield strength of the phase-change Ti-based amorphous composite material by adding Al.
The technical scheme of the invention is as follows:
a method for improving the strength of phase-change Ti-based amorphous composite material by adding Al is disclosed, the composite material is Ti-based amorphous endogenetic composite material, and the composition of the composite material follows (Ti) according to atomic percentage0.474Zr0.34Cu0.06Be0.126)100-xAlxWhere x is 0, 4, 6 or 8, and is simply referred to as Alx alloy.
In the method for improving the strength of the phase-change Ti-based amorphous composite material by adding Al, an amorphous matrix of the phase-change Ti-based amorphous composite material has high glass forming capacity, and an alloy cast by a copper mold is an amorphous endogenetic composite material tissue; the technical indexes for representing the forming capability of the amorphous matrix glass are as follows: the phase-change Ti-based amorphous composite material is cast by a copper mold to obtain a round bar sample with the diameter of 12mm, and an amorphous matrix is not crystallized.
The method for improving the strength of the phase-change Ti-based amorphous composite material by adding Al comprises the following steps: the endogenous beta-Ti phase in the amorphous composite material is a metastable phase and can generate deformation induced alpha '/alpha' martensite phase transformation in the stretching deformation process.
The method for improving the strength of the phase-change Ti-based amorphous composite material by adding Al has different deformation mechanisms along with different Al contents; the plastic deformation mechanism of beta-Ti in Al0 and Al4 is deformation-induced martensite transformation and twin crystal, and the plastic deformation mode of beta-Ti in Al6 and Al8 is dislocation mechanism.
According to the method for improving the strength of the phase-change Ti-based amorphous composite material by adding the Al, the tensile yield strength of the phase-change Ti-based amorphous composite material is obviously and monotonically increased by adding the Al element: 795 +/-15 MPa of Al0 alloy, 1190 +/-20 MPa of Al4 alloy, 1340 +/-15 MPa of Al6 alloy and 1470 +/-22 MPa of Al8 alloy.
The method for improving the strength of the phase-change Ti-based amorphous composite material by adding Al comprises the following steps: (1) the stability of the endogenous beta-Ti is improved by adding Al; (2) al addition results in the formation of covalent-like bonds of high bonding strength.
According to the method for improving the strength of the phase-change Ti-based amorphous composite material by adding Al, in the phase-change Ti-based amorphous composite material, the plastic deformation capacity of the amorphous composite material is improved while the tensile yield strength of the amorphous endogenetic composite material is improved by adding a small amount of Al: the addition of 4 at.% Al resulted in an increase in tensile strain from 6.9% of Al0 to 8% of Al 4.
The principle of the Al-added reinforced phase-change Ti-based amorphous composite material is as follows:
the physical mechanism for improving the yield strength of the phase-change Ti-based amorphous composite material by adding Al comprises the following steps: on one hand, the addition of Al can improve the stability of the endogenous metastable beta-Ti phase; on the other hand, after Al is added, a higher-strength covalent-like bond can be formed, the covalent-like bond is different from a metal bond formed by 'free electron gas' in metals and alloys, but has directionality in the process of electron orbital hybridization of Al atoms and other constituent atoms, and has similar characteristics with the covalent bond, and the bond has higher strength. These two mechanisms are described in detail below:
al addition to improve stability of endogenous metastable beta-Ti phase
After the amorphous endogenetic composite material is added with the Al element, the Al element changes the partition coefficient of each component between the amorphous matrix phase and the endogenetic beta-Ti phase. Resulting in an increase in the content of Cu element in β -Ti from 2.1% in Al0 to 2.4% in Al4, 2.7% in Al6, and 3.2% in Al8 (all atomic%). The Zr content in β -Ti decreased from 34.7% in Al0 to 33.2% in Al4, 32% in Al6, and 31% in Al 8. The specific contents of the elements in the two phases are shown in the attached table 1.
TABLE 1 content of Components in amorphous endogenetic composite
Figure GDA0002944952270000031
Both factors contribute to the improvement of the stability of beta-Ti. The increased stability of β -Ti means that the transformation to the α "-Ti martensite phase is more difficult, i.e. Al addition results in Δ Gβ→α"increase. Yield strength of phase-change amorphous endogenetic composite material
Figure GDA0002944952270000032
Comprises the following steps:
Figure GDA0002944952270000033
wherein
Figure GDA0002944952270000034
C3＝1-Vβ。ΔGβ→α"is the difference between the free energy of the beta phase and the alpha" phase, and is an important parameter for measuring the stability of the endogenous beta phase.
Figure GDA0002944952270000035
Is the yield strength of the amorphous matrix. VβIs the volume fraction of beta-Ti phase in the amorphous endogenetic composite material,
Figure GDA0002944952270000036
is the strain under which the martensitic transformation occurs under unconstrained conditions,
Figure GDA0002944952270000037
is that
Figure GDA0002944952270000038
Component in the loading direction.
Figure GDA0002944952270000039
Is the average molar volume of β -Ti and α "-Ti.
Figure GDA00029449522700000310
Is determined by the following formula:
Figure GDA00029449522700000311
wherein
Figure GDA00029449522700000312
K and G are the bulk modulus (GPa) and the shear modulus (GPa) of beta-Ti, respectively. For the Alx amorphous endogenetic composite material, the size and the shape of endogenetic beta-Ti are similar, so C1、C2And C3May be considered constant.
As can be seen from the formula (1), the phase stability of β -Ti increases with the addition of Al element, i.e., Δ Gβ→α"increase" which directly results in an increase in yield strength of the amorphous endogenetic composite, thereby achieving reinforcement.
(II) Al addition to form high strength covalent-bond-like bonds
Due to the special chemical property of the Al element, Al atoms are easy to form covalent bond-like combination with transition group metal atoms in the alloying process, and the atomic bond is different from common metal bonds and has higher strength. With the addition of Al content, the nano indentation hardness value of the amorphous matrix is increased from 6.6 +/-0.3 GPa in Al0 to 7.1 +/-0.2 GPa in Al4, 7.2 +/-0.3 GPa in Al6 and 7.2 +/-0.2 GPa in Al 8. The mechanism is also the reason for improving the yield strength of the amorphous endogenetic composite material by adding Al.
The invention has the advantages and beneficial effects that:
(1) according to the invention, by adding Al element, the yield strength of the phase-change type Ti-based amorphous endogenetic composite material can be obviously improved, so that the material reinforcement is realized. The method is low in cost, simple and effective, and has wide universality for strengthening the phase-change type Ti-based amorphous endogenetic composite material.
(2) According to the Ti-Zr-Cu- (Al) -Be amorphous endogenetic composite material, an amorphous matrix has high glass forming capacity, a large size is easy to obtain, and an alloy rod with the copper mold casting diameter of 12mm is an amorphous composite material structure.
(3) The Ti-Zr-Cu- (Al) -Be amorphous endogenous composite material has excellent tensile mechanical properties, including obviously improved yield strength, larger tensile plasticity and work hardening capacity.
In conclusion, the influence of the Al element on the stability of the beta-Ti phase in the composite material is systematically researched by adjusting the content of the Al element. It was found that the tensile yield strength of the amorphous green composite increased significantly with increasing Al content. The research of the system shows that the addition of the Al element increases the structural metastability of the endogenous metastable beta-Ti on one hand, and the Al element and other transition group metal components are easy to form covalent bonds with high strength on the other hand, and the yield strength of the phase-change type Ti-based amorphous endogenous composite material is remarkably increased along with the increase of the Al content.
Description of the drawings:
FIG. 1 is an X-ray diffraction spectrum of an as-cast structure of an alloy rod of 12mm in diameter.
FIG. 2 is a scanning electron micrograph of the as-cast structure of an Alx amorphous endogenetic composite. Wherein (a) represents Al0, (b) represents Al4, (c) represents Al6, and (d) represents Al 8.
FIG. 3 is a transmission electron micrograph of the as-cast structure of Al0, Al4, and Al 6. Wherein (a) represents Al0, (b) represents Al4, and (c) represents Al 6.
FIG. 4 is a tensile true stress-strain curve of an Alx amorphous endogenetic composite.
FIG. 5 is an X-ray diffraction spectrum of the Al amorphous endogenetic composite after tensile failure.
FIGS. 6(a) and (b) are SEM micrographs after tensile failure of Al0 and Al4, respectively, and FIGS. 6(c) and (d) are TEM micrographs after tensile failure of Al0 and Al8, respectively.
Detailed Description
In the specific implementation process, the method for improving the strength of the phase-change Ti-based amorphous composite material by adding Al comprises the following steps:
the phase-change type Ti-based amorphous composite material is Ti-Zr-Cu- (Al) -Be alloy, and the component range of the phase-change type Ti-based amorphous composite material is simulated and changed according to the following component proportion: (Ti)0.474Zr0.34Cu0.06Be0.126)100-xAlx(all atomic percentages) where x is 0, 4, 6, 8, and is abbreviated as Alx alloy according to the different Al contents.
The raw materials are sponge Ti and sponge Zr with industrial purity, and the purity of the rest elements is higher than 99.8 wt%. Preparing an alloy ingot by an arc melting method in a high-purity argon (volume purity of 99.999 percent and 0.01-0.1 MPa) environment, and repeatedly melting the alloy ingot for at least four times to ensure the uniformity of components. Then remelting alloy ingots in an electric arc furnace in a high-purity argon environment, and obtaining alloy rods with the diameter of 12mm in a copper mold turnover casting mode. Tensile specimens with gauge dimensions of 14mm by 2mm by 0.8mm were cut from the alloy rods and subjected to microstructural characterization.
Through mechanical property tests and microstructure detection, the stability of the endogenous beta-Ti phase is gradually increased along with the increase of Al content, and the endogenous beta-Ti phase is converted into a stable beta phase from a metastable beta-Ti phase which can generate deformation to induce martensite phase transformation, and the plastic deformation mechanism of the endogenous beta-Ti phase is specifically as follows: the transformation from the martensite transformation mechanism to the dislocation slip mechanism is mainly induced by deformation in Al0 and Al4, and mainly occurs in Al6 and Al 8.
The performance indexes of the phase-change Ti-based amorphous composite material are as follows:
tensile yield strength: 795 +/-15 MPa (Al0), 1190 +/-20 MPa (Al4), 1340 +/-15 MPa (Al6) and 1470 +/-22 MPa (Al8), namely obviously increasing monotonously. Tensile strain: 6.9 plus or minus 0.2 percent (Al0), 8 plus or minus 0.3 percent (Al4), 4.0 plus or minus 0.2 percent (Al6) and 3.1 plus or minus 0.2 percent (Al8), namely increasing and then decreasing.
The present invention will be described in detail below with reference to examples.
Example 1
This example (Ti)0.474Zr0.34Cu0.06Be0.126)100-xAlxIn the alloy system, x is 0 and 4, namely Al0 and Al4 alloy, the raw materials of Ti and Zr adopt sponge Ti and sponge Zr with industrial purity, and the purity of the rest elements is higher than 99.8 wt%. Placing the raw materials in the order of decreasing the melting point from top to bottom, and pumping the pressure in the furnace to 1.0 × 10 by using a mechanical pump and a molecular pump-3Pa～3.0×10-3Pa, introducing high-purity Ar gas to about 0.05MPa, preparing a master alloy ingot by an arc melting method under the protection of argon, and repeatedly melting the alloy ingot for five times. The alloy rod with the diameter of 12mm and the length of 55mm is obtained by casting in a turning furnace. The alloy bar was cut by wire electric discharge machining and a speed saw to obtain a drawing pattern having a drawing pattern size of 14mm × 2mm × 0.8 mm. The stretching sample is ground and polished by sand paper and polishing liquid, so that the organization structure of the material is conveniently and accurately characterized.
The as-cast rods were sliced to a thickness of about 1mm and the as-cast tissue was characterized. The as-cast structure of the Al0 alloy is shown in fig. 1, in which some of the hetero peaks, i.e., the peaks of the α "phase, are observed in addition to the peaks of the β phase, but as the Al content increases, these hetero peaks have disappeared in the Al4 alloy, demonstrating that the structure of the Al4 alloy is transformed and the alloy β phase stability is changed. It is worth mentioning how much the brightness of the transmitted electron diffraction spot of fig. 3 reflects the content of the omega phase inside the alloy. The diffraction spot in fig. 3(a) is clearly brighter than the spot in (b), reflecting that ω is less in Al0 than in Al 4. Since the omega phase can be thought of as resulting from lattice collapse of the beta phase, the reduction in omega phase again demonstrates the improvement in beta phase stability. The Al4 alloy has transformed from the highly metastable state to the less metastable state of Al 0.
From fig. 2(a), (b), the distribution of the dendritic phase and the amorphous matrix is seen, wherein the dendritic matrix occupies about 60% of the total volume, and the volume fraction of the dendritic phase is not significantly affected by the change of Al content. In this embodiment, in the phase-change Ti-based amorphous composite material, the amorphous matrix has high glass forming ability, and the technical indexes characterizing the glass forming ability of the amorphous matrix are as follows: the two alloys can be cast by a copper mould to obtain a round bar sample with the diameter of 12mm, and an amorphous matrix is not crystallized.
In FIG. 4, the true stress-strain curves of the Al0 and Al4 alloys under tensile stress are shown, and the strong work hardening capacity of the Al0 alloy can be seen. The yield strength of the Al4 alloy is about 1200MPa, which is obviously higher than that of Al0, the yield strength of the alloy is about 800MPa, and the plasticity of the whole alloy is obviously improved and reaches about 8 percent when the alloy undergoes three times of yield processes and shows in the stretching process. From the results of the X-ray diffraction spectrum in fig. 5, it can be seen that new phases are generated in both Al0 and Al4 alloys during the deformation process, and the transmission electron microscope image in fig. 6(c) can prove that the alloys have martensite phase transformation and generate a large amount of twin crystal structures during the deformation process. However, the two are still different, and it is found from the scanning electron microscope images in fig. 6(a) and (b) that the dendritic phase in the vicinity of the fracture contains a significantly reduced martensite lath relief structure, which also means that the dendritic phase of Al4 alloy is somewhat more stable than that of Al0 alloy.
Example 2
This example (Ti)0.474Zr0.34Cu0.06Be0.126)100-xAlxIn the alloy system, x is 6 and 8, namely Al6 and Al8 alloy, the raw materials of Ti and Zr adopt sponge Ti and sponge Zr with industrial purity, and the purity of the rest elements is higher than 99.8 wt%. Placing the raw materials in the order that the melting points are reduced from top to bottom, pumping the furnace body to below 1Pa by using a mechanical pump, and then pumping the internal pressure of the furnace to 1.0 multiplied by 10 by using a molecular pump-3Pa～3.0×10-3Introducing high-purity Ar gas below Pa to about 0.03MPa, and arc melting under the protection of argon to obtain mother alloy ingotThe smelting is repeated eight times. The alloy rod with the diameter of 12mm and the length of 55mm is obtained by casting in a turning furnace. The alloy bar was cut by wire electric discharge machining and a speed saw to obtain a drawing pattern having a drawing pattern size of 14mm × 2mm × 0.8 mm. The stretching sample is ground and polished by sand paper and polishing liquid, so that the organization structure of the material is conveniently and accurately characterized.
The as-cast rods were sliced to a thickness of about 1mm and the as-cast tissue was characterized. From fig. 1, it can be seen that the microstructure of the Al6 and Al8 alloys is composed of a β phase and an amorphous matrix, and no other peaks occur. In this embodiment, in the phase-change Ti-based amorphous composite material, the amorphous matrix has high glass forming ability, and the technical indexes characterizing the glass forming ability of the amorphous matrix are as follows: the Al6 and Al8 alloy can obtain round bar samples with the diameter of 12mm through copper die casting, and an amorphous matrix is not crystallized.
The electron diffraction of fig. 3(c) also further demonstrates that Al6 has no ω -phase composition, and that the β -phase in the alloy has a stable BCC structure. From the structure of the as-cast structure, it can be seen that the stability of the β phase is sufficiently improved with the increase of the Al content, and Al6 is an amorphous endogenetic composite material having a stable β phase structure. The content change of the elements in the beta phase can be detected by an energy spectrum carried by a scanning electron microscope: the Cu element in the Al6 and Al8 alloys is obviously improved, the Cu element is used as a beta phase stabilizing element in the Ti alloy, the stability of the beta phase is obviously influenced by the increase of the content of the Cu element, and a basis is provided for the stabilization of the beta phase in the Alx alloy.
The tensile true stress-strain curves of the Al6, Al8 alloys can be seen in fig. 4, with the Al6 alloy having a yield strength (about 1400MPa) exceeding that of typical composites, and the Al8 alloy having the highest yield strength Ti-based amorphous in-grown composites found to date with a yield strength around 1600 MPa. Fig. 6(d) is a representation of the microstructure of the Al8 alloy after deformation, and it can be seen that the dendritic phase of the Al8 alloy does not undergo a phase change after deformation, but rather produces a number of deformed band structures that are actually dislocation structures. This is in contrast to the Al0 alloy, which has undergone a significant change in the deformation mechanism due to a complete transformation in the beta phase stability.
The embodiment result shows that the invention discovers that the Al element changes the component partition coefficients of other components in beta-Ti and amorphous matrix by adjusting the content of the Al element, thereby realizing the improvement of the phase stability of the beta-Ti; in addition, Al atoms themselves and other atoms readily form covalent-like bonds with higher strength. Due to the two factors, the yield strength of the phase-change Ti-based amorphous endogenetic composite material can be remarkably improved by adding Al, and the method has important value for development and application of the amorphous composite material.

Claims (7)

1. A method for improving the strength of a phase-change Ti-based amorphous composite material by adding Al is characterized in that the composite material is a Ti-based amorphous endogenetic composite material, and the composition of the composite material follows (Ti) according to atomic percentage0.474Zr0.34Cu0.06Be0.126)100-xAlxWhere x is 4, 6 or 8, and is simply referred to as Alx alloy.
2. The method for improving the strength of the phase-change Ti-based amorphous composite material by adding Al according to claim 1, wherein in the phase-change Ti-based amorphous composite material, an amorphous matrix has high glass forming capability, and an alloy cast by a copper mold is an amorphous endogenous composite material structure; the technical indexes for representing the forming capability of the amorphous matrix glass are as follows: the phase-change Ti-based amorphous composite material is cast by a copper mold to obtain a round bar sample with the diameter of 12mm, and an amorphous matrix is not crystallized.
3. The method for improving the strength of the phase-change Ti-based amorphous composite material by adding Al according to claim 1, wherein the phase-change Ti-based amorphous composite material is characterized in that: the endogenous beta-Ti phase in the amorphous composite material is a metastable phase and can generate deformation induced alpha '/alpha' martensite phase transformation in the stretching deformation process.
4. The method for improving the strength of the phase-change Ti-based amorphous composite material by adding Al according to claim 1, wherein the phase-change Ti-based amorphous composite material has different deformation mechanisms with different Al contents; the plastic deformation mechanism of beta-Ti in Al0 and Al4 is deformation-induced martensite transformation and twin crystal, and the plastic deformation mode of beta-Ti in Al6 and Al8 is dislocation mechanism.
5. The method for improving the strength of the phase-change Ti-based amorphous composite material by adding Al in claim 1, wherein the tensile yield strength of the phase-change Ti-based amorphous composite material is increased obviously and monotonously by adding Al element: 795 +/-15 MPa of Al0 alloy, 1190 +/-20 MPa of Al4 alloy, 1340 +/-15 MPa of Al6 alloy and 1470 +/-22 MPa of Al8 alloy.
6. The method for improving the strength of the phase-change Ti-based amorphous composite material by adding Al according to claim 5, wherein the mechanism for adding Al to strengthen the phase-change Ti-based amorphous composite material comprises the following steps: (1) the stability of the endogenous beta-Ti is improved by adding Al; (2) al addition results in the formation of covalent-like bonds of high bonding strength.
7. The method for improving the strength of the phase-change Ti-based amorphous composite material by adding Al according to claim 1, wherein in the phase-change Ti-based amorphous composite material, the addition of a small amount of Al element improves the tensile yield strength of the amorphous endogenetic composite material and also improves the plastic deformation capacity of the amorphous composite material: the addition of 4 at.% Al resulted in an increase in tensile strain from 6.9% of Al0 to 8% of Al 4.
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CN106567015A (en) * 2016-11-21 2017-04-19 中国科学院金属研究所 CuZr-based bulk amorphous alloy and preparation method and application thereof
CN107385365A (en) * 2017-06-26 2017-11-24 中国科学院金属研究所 Ti Zr Cu Be quaternary amorphous composite materials with work hardening capacity and preparation method thereof
CN108165900A (en) * 2018-01-11 2018-06-15 深圳大学 Titanium-based amorphous alloy spectacle frame and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0573484B1 (en) * 1991-02-25 1999-09-15 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Titanium-based alloy produced by vapour quenching
CN1122148A (en) * 1993-04-07 1996-05-08 加利福尼亚技术学院 Formation of beryllium containing metallic glasses
CN102296253A (en) * 2010-06-23 2011-12-28 中国科学院金属研究所 Internal-flexibility phase-enhanced Ti-base amorphous composite material and preparation method thereof
CN106567015A (en) * 2016-11-21 2017-04-19 中国科学院金属研究所 CuZr-based bulk amorphous alloy and preparation method and application thereof
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CN108165900A (en) * 2018-01-11 2018-06-15 深圳大学 Titanium-based amorphous alloy spectacle frame and preparation method thereof

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