CN115637395A - High-hardness large-size zirconium-based amorphous alloy with plastic deformation and preparation method thereof - Google Patents
High-hardness large-size zirconium-based amorphous alloy with plastic deformation and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of amorphous alloy, and particularly relates to a high-hardness large-size zirconium-based amorphous alloy with plastic deformation and a preparation method thereof, wherein the atomic percentage expression of the high-hardness large-size zirconium-based amorphous alloy is as follows: zr a Cu b Ni c Al d Ti e Nb f Hf g M r (ii) a Wherein a + b + c + d + e + f + g + r =100; m is a rare earth element; and 50 < a < 65; b is more than 10 and less than 20; c is more than 5 and less than 15; d is more than 5 and less than 15; e is more than or equal to 0 and less than 10; f is more than or equal to 0 and less than 10; g is more than 0 and less than 2; r is more than 0 and less than 0.5; the high-hardness large-size zirconium-based amorphous alloy with plastic deformation and the preparation method thereof utilize the characteristic that rare earth elements preferentially react with oxygen elements, and industrial raw materials are adopted without worrying about the damage of the oxygen elements to the amorphous forming capacity; the joint addition of Nb, ti and Hf also increases the configuration entropy and the mixed entropy of the system, and simultaneously forms strong clusters in the Zr-Cu-Ni-Al-Ti system, thereby causing the nonuniformity of free volumeThe distribution is even, and the plasticity and the hardness of the material are improved while the forming capability of the amorphous alloy is improved.
Description
Technical Field
The invention belongs to the technical field of amorphous alloys, and particularly relates to a high-hardness large-size zirconium-based amorphous alloy with plastic deformation and a preparation method thereof.
Background
The amorphous alloy is used as a novel alloy material which is different from conventional alloys, and the unique structure of the amorphous alloy enables the amorphous alloy to have the performance which is different from that of the conventional alloys, such as high strength, high hardness, high corrosion resistance, self-sharpening property and the like, so that the amorphous alloy has wide application prospects in military, medical instruments, sports goods, electronic product parts, precision parts and the like.
However, the same disadvantage is also true for amorphous alloys, although amorphous alloys have higher strength and hardness, most of the amorphous alloys have brittle fracture, only a few amorphous alloys have certain plasticity, and amorphous alloys with plasticity are often weaker in hardness and forming ability, thus causing a barrier to the application and development of amorphous alloys.
The development of the amorphous alloy with high hardness and certain plasticity has a great propulsion effect on the application of the amorphous alloy in the fields of high-precision parts, elastic parts, 3C electronics and the like.
Disclosure of Invention
The invention provides a high-hardness large-size zirconium-based amorphous alloy with plastic deformation and a preparation method thereof, which aim to solve the problem that the hardness of the amorphous alloy with the plastic deformation is insufficient.
In order to solve the technical problems, the invention provides a high-hardness large-size zirconium-based amorphous alloy with plastic deformation, which comprises the following atomic percentage expressions: zr a Cu b Ni c Al d Ti e Nb f Hf g M r (ii) a Wherein a + b + c + d + e + f + g + r =100; m is a rare earth element; and 50 < a < 65; b is more than 10 and less than 20; c is more than 5 and less than 15; d is more than 5 and less than 15; e is more than or equal to 0 and less than 10; f is more than or equal to 0 and less than 10; g is more than 0 and less than 2; r is more than 0 and less than 0.5.
In another aspect, the present invention further provides a method for preparing a high-hardness large-size zirconium-based amorphous alloy having plastic deformation, comprising the steps of: step S1, converting the components into mass ratios according to the atomic percentages in claim 1, and weighing and preparing the raw materials; s2, performing electric arc premelting on the refractory metal, hf and part of Zr to obtain a premelted material; s3, performing vacuum induction melting on the pre-melted material and the rest raw materials for 4-5 times until the materials are uniformly melted, and taking out the materials after the materials are completely cooled to obtain a material block; and S4, polishing the material block, and then die-casting the material block in a vacuum induction copper mold to obtain the high-hardness large-size zirconium-based amorphous alloy with plastic deformation.
The invention has the advantages that the high-hardness large-size zirconium-based amorphous alloy with plastic deformation and the preparation method thereof utilize the characteristic of preferential reaction of rare earth elements to oxygen elements, and industrial raw materials are adopted without worrying about the damage of the oxygen elements to the amorphous forming capacity; the joint addition of Nb, ti and Hf also increases the configuration entropy and the mixed entropy of the system, and forms strong clusters in the Zr-Cu-Ni-Al-Ti system, thereby causing the uneven distribution of free volume, and improving the plasticity and hardness of the material while increasing the forming capability of the amorphous alloy.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an XRD pattern of 5mm rods of examples 1 to 4 of a high-hardness large-size zirconium-based amorphous alloy having plastic deformation according to the present invention;
FIG. 2 is an XRD pattern of 5mm rods of examples 5 to 7 of a high-hardness large-size zirconium-based amorphous alloy having plastic deformation according to the present invention;
FIG. 3 is an XRD pattern of a 3mm rod of comparative example 1 of a high-hardness large-size zirconium-based amorphous alloy having plastic deformation according to the present invention;
FIG. 4 is a stress-strain curve of 4mm rods of examples 1-4 of the high hardness large size zirconium based amorphous alloy with plastic deformation according to the present invention;
FIG. 5 is a stress-strain curve of 4mm rods of examples 5 to 7 of a high-hardness large-size zirconium-based amorphous alloy having plastic deformation according to the present invention;
FIG. 6 is a stress-strain curve of the 3mm rod of comparative example 1 of a high-hardness large-size zirconium-based amorphous alloy having plastic deformation according to the present invention.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a high-hardness large-size zirconium-based amorphous alloy with plastic deformation, which comprises the following atomic percent expressions: zr a Cu b Ni c Al d Ti e Nb f Hf g M r (ii) a Wherein a + b + c + d + e + f + g + r =100; m is a rare earth element; and 50 < a < 65; b is more than 10 and less than 20; c is more than 5 and less than 15; d is more than 5 and less than 15; e is more than or equal to 0 and less than 10; f is more than or equal to 0 and less than 10; g is more than 0 and less than 2; r is more than 0 and less than 0.5.
In this embodiment, specifically, the melting point of Hf is as high as 2233 ℃, the Hf belongs to a refractory metal, the refractory metal is also called a high-melting rare metal, the melting point is high in hardness and high in corrosion resistance, and since Hf is a sixth-period transition element, the energy level of an outer-layer electron s electron is close to that of a second outer-layer d electron, so that the d electrons can partially or completely participate in bonding to form a plurality of oxidation numbers, and the Hf is compounded into the amorphous alloy system of the present invention, so that the amorphous alloy obtains a natural amorphous oxide layer with uniformly distributed components, and meanwhile, the part of the refractory metal is in disordered arrangement during melting, defects of grain boundaries, dislocation, segregation and the like of the original metal are eliminated, and the part of the refractory metal is used as a trace additive element to form an amorphous alloy with other components, so that the amorphous alloy of the present invention has the advantages of the refractory high-entropy alloy material and the amorphous alloy, and is specifically expressed as excellent hardness.
In this embodiment, specifically, the atomic percent content of Ti is 0 to 10, and the atomic percent content of refractory metal such as Hf is 0 to 2, and the existence of both increases the configuration entropy and the mixing entropy of the system, and forms strong clusters in the Zr-Cu-Ni-Al-Ti system, thereby causing uneven distribution of free volume, and increasing the plasticity and hardness of the material while increasing the amorphous alloy forming ability.
In this embodiment, specifically, the atomic percentage content of Nb is 0 to 10, the amorphous alloy in this region has high thermal stability and amorphous forming ability, and the addition of Nb increases the number of system components in the Zr-Cu-Ni-Al-Ti system, increases the degree of disorder of atomic accumulation in the system, and makes it more difficult to rearrange atoms required for crystallization, so that the supercooled liquid of the amorphous alloy has higher thermal stability; meanwhile, due to the addition of Nb, the size change of the component atoms is more continuous, namely Zr & gt Nb & gt Al & gt Ni & gt Cu, and the bulk density of an amorphous phase is further improved; meanwhile, the addition of Nb also has negative mixed heat with Ni and Al in the original system, so that a new mutually-attracted coupling atom pair is formed inside the system, the interatomic force is more complex, the crystallization requires long-range diffusion of atoms to meet the requirements of components and structures of the atoms, and the more complex interatomic force and the more disordered atom accumulation play an important role in inhibiting the atom diffusion. Furthermore, the formation of the repulsive coupling atom pair in the amorphous alloy system also improves the plastic deformation capability of the bulk amorphous alloy, and simultaneously does not reduce the amorphous forming capability and the thermal stability of the amorphous alloy, and it should be noted that when the atomic percentage content of Nb is greater than 10, the crystallization mode of the bulk amorphous is changed from single-step crystallization to multi-step crystallization, and the amorphous forming capability is greatly reduced.
In this embodiment, specifically, the M includes Y, dy, lu, ho, yb, ce, rh, and on one hand, since the refractory metal has a high melting point, the material system has a large viscosity, a poor fluidity, and a large size difference between atoms, lattice distortion is easily caused, and the amorphous forming ability is poor, the rare earth element is selected to be compounded with the main element to improve the amorphous forming ability, and the defect of the decrease of the amorphous alloy forming ability caused by the addition of the refractory metal is eliminated; on the other hand, oxygen element, which is a harmful element to the forming capability of the amorphous alloy, is inevitably doped in the process from the raw material to the forming of the amorphous alloy, and rare earth elements such as Y can effectively reduce the oxygen element in the alloy components, and the rare earth elements can preferentially react with the oxygen element in the smelting process, so that the influence of oxygen is reduced, and the forming capability of the amorphous alloy is improved.
In the present embodiment, specifically, the amorphous forming ability of the high-hardness large-size zirconium-based amorphous alloy having plastic deformation is not less than 5mm.
In the present embodiment, in particular, the compressive strength of the high-hardness large-size zirconium-based amorphous alloy having plastic deformation is not less than 1600MPa.
In this embodiment, specifically, the hardness Hv 0.5 of the high-hardness large-size zirconium-based amorphous alloy having plastic deformation is not less than 580.
In the present embodiment, specifically, the plastic elongation of the high-hardness large-size zirconium-based amorphous alloy having plastic deformation is not less than 4%.
The invention also provides a preparation method of the high-hardness large-size zirconium-based amorphous alloy with plastic deformation, which comprises the following steps: step S1, converting the components into mass ratios according to the atomic percentages in claim 1, and weighing and preparing the raw materials; s2, performing electric arc premelting on the refractory metal, hf and part of Zr to obtain a premelted material; s3, performing vacuum induction melting on the pre-melted material and the rest raw materials for 4-5 times until the materials are uniformly melted, and taking out the materials after the materials are completely cooled to obtain a material block; and S4, polishing the material block, and then die-casting the material block in a vacuum induction copper mold to obtain the high-hardness large-size zirconium-based amorphous alloy with plastic deformation.
In this embodiment, specifically, the vacuum induction melting in step S3 includes: vacuum degree not greater than 10 -1 MPa; the protective gas comprises Ar and N 2 。
The implementation examples of the invention are as follows:
example 1
The titanium-based amorphous alloy prepared by the embodiment comprises the following components: zr 55.4 Cu 17.9 Al 9.3 Ni 12.5 Ti 4 Hf 0.5 Y 0.3 Ho 0.1 The preparation method comprises the following steps:
(1) Weighing the components in proportion, firstly smelting part of Zr and Hf by adopting an electric arc or high-temperature vacuum smelting furnace, and cooling and taking out after the Zr and Hf are completely molten.
(2) Adding the pre-melted Zr-Hf and the rest raw materials into an electric arc melting furnace, melting for 4-5 times, cooling to room temperature after the metal is uniformly melted, and taking out a material block.
(3) And (4) polishing the material block, and cleaning surface oxides.
(4) And (3) intercepting proper raw materials, carrying out vacuum induction copper die casting, and preparing alloy bars with diameters of 4mm and 5mm by adopting a copper die.
Example 2
The composition of the zirconium-based amorphous alloy prepared by the embodiment is as follows: zr 56 Cu 17.6 Al 9.2 Ni 12.4 Ti 4 Hf 0.5 Y 0.2 Ho 0.1 The preparation method comprises the following steps:
(1) Weighing the components in proportion, firstly smelting part of Zr and Hf by adopting an electric arc or high-temperature vacuum smelting furnace, and cooling and taking out after the Zr and Hf are completely molten.
(2) Adding the pre-melted Zr-Hf and the rest raw materials into an electric arc melting furnace, melting for 4-5 times, cooling to room temperature after the metal is uniformly melted, and taking out a material block.
(3) And (5) polishing the material blocks to clean surface oxides.
(4) And (3) intercepting proper raw materials, carrying out vacuum induction copper die casting, and preparing alloy bars with diameters of 4mm and 5mm by adopting a copper die.
Example 3
The composition of the zirconium-based amorphous alloy prepared by the embodiment is as follows: zr 51 Cu 18.5 Al 9.7 Ni 14 Ti 6 Hf 0.5 Y 0.2 Ho 0.1
The preparation method comprises the following steps:
(1) Weighing the components in proportion, smelting part of Zr and Hf by adopting an electric arc or high-temperature vacuum smelting furnace, and cooling and taking out after the Zr and the Hf are completely smelted.
(2) Adding the pre-melted Zr-Hf and the rest raw materials into an electric arc melting furnace, melting for 4-5 times, cooling to room temperature after the metal is uniformly melted, and taking out a material block.
(3) And (5) polishing the material blocks to clean surface oxides.
(4) And (3) intercepting proper raw materials, carrying out vacuum induction copper die casting, and preparing alloy bars with diameters of 4mm and 5mm by adopting a copper die.
Example 4
The composition of the zirconium-based amorphous alloy prepared by the embodiment is as follows: zr 51.4 Cu 18.3 Al 9.5 Ni 14 Ti 6 Hf 0.6 Y 0.2
The preparation method comprises the following steps:
(1) Weighing the components in proportion, firstly smelting part of Zr and Hf by adopting an electric arc or high-temperature vacuum smelting furnace, and cooling and taking out after the Zr and Hf are completely molten.
(2) Adding the pre-melted Zr-Hf and the rest raw materials into an electric arc melting furnace, melting for 4-5 times, cooling to room temperature after the metal is uniformly melted, and taking out a material block.
(3) And (5) polishing the material blocks to clean surface oxides.
(4) And (3) intercepting proper raw materials, carrying out vacuum induction copper die casting, and preparing alloy bars with diameters of 4mm and 5mm by adopting a copper die.
Example 5
The titanium-based amorphous alloy prepared by the embodiment comprises the following components: zr 57.5 Cu 16 Al 10 Ni 12.8 Nb 2.7 Hf 0.6 Y 0.3 Ho 0.1
The preparation method comprises the following steps:
(1) Weighing the components in proportion, firstly smelting part of Zr, nb and Hf by adopting an electric arc or high-temperature vacuum smelting furnace, and cooling and taking out after the Zr, nb and Hf are completely smelted.
(2) Adding the pre-melted Zr-Hf-Nb and the rest raw materials into an electric arc melting furnace, melting for 4-5 times, cooling to room temperature after the metal is uniformly melted, and taking out a material block.
(3) And (5) polishing the material blocks to clean surface oxides.
(4) And (3) intercepting proper raw materials, carrying out vacuum induction copper die casting, and preparing alloy bars with diameters of 4mm and 5mm by adopting a copper die.
Example 6
The composition of the zirconium-based amorphous alloy prepared by the embodiment is as follows: zr 55.4 Cu 15.4 Al 9 Ni 13.5 Nb 4 Ti 2 Hf 0.5 Y 0.2
The preparation method comprises the following steps:
(1) Weighing the components in proportion, smelting part of Zr, nb and Hf by adopting an electric arc or high-temperature vacuum smelting furnace, and cooling and taking out after the Zr, nb and Hf are completely smelted.
(2) Adding the pre-melted Zr-Hf-Nb and the rest raw materials into an electric arc melting furnace, melting for 4-5 times, cooling to room temperature after the metal is uniformly melted, and taking out a material block.
(3) And (5) polishing the material blocks to clean surface oxides.
(4) And (3) intercepting proper raw materials, carrying out vacuum induction copper die casting, and preparing alloy bars with diameters of 4mm and 5mm by adopting a copper die.
Example 7
The composition of the zirconium-based amorphous alloy prepared by the embodiment is as follows: zr 57.4 Cu 15.4 Al 9 Ni 11.5 Nb 4 Ti 2 Hf 0.5 Y 0.2
The preparation method comprises the following steps:
(1) Weighing the components in proportion, firstly smelting part of Zr, nb and Hf by adopting an electric arc or high-temperature vacuum smelting furnace, and cooling and taking out after the Zr, nb and Hf are completely smelted.
(2) Adding the pre-melted Zr-Hf-Nb and the rest raw materials into an electric arc melting furnace, melting for 4-5 times, cooling to room temperature after the metal is uniformly melted, and taking out a material block.
(3) And (4) polishing the material block, and cleaning surface oxides.
(4) And (3) intercepting proper raw materials, carrying out vacuum induction copper die casting, and preparing alloy bars with diameters of 4mm and 5mm by adopting a copper die.
Example 8
The composition of the zirconium-based amorphous alloy prepared by the embodiment is as follows: zr 63.1 Cu 12.7 Al 6.2 Ni 6.5 Nb 3 Ti 8 Hf 0.3 Y 0.2
The preparation method comprises the following steps:
(1) Weighing the components in proportion, firstly smelting part of Zr, nb and Hf by adopting an electric arc or high-temperature vacuum smelting furnace, and cooling and taking out after the Zr, nb and Hf are completely smelted.
(2) Adding the pre-melted Zr-Hf-Nb and the rest raw materials into an electric arc melting furnace, melting for 4-5 times, cooling to room temperature after the metal is uniformly melted, and taking out a material block.
(3) And (5) polishing the material blocks to clean surface oxides.
(4) And (3) intercepting proper raw materials, carrying out vacuum induction copper die casting, and preparing alloy bars with diameters of 4mm and 5mm by adopting a copper die.
Example 9
The composition of the zirconium-based amorphous alloy prepared by the embodiment is as follows: zr 52 Cu 12.2 Al 7.2 Ni 8.6 Nb 9.7 Ti 8.6 Hf 1.5 Y 0.2
The preparation method comprises the following steps:
(1) Weighing the components in proportion, firstly smelting part of Zr, nb and Hf by adopting an electric arc or high-temperature vacuum smelting furnace, and cooling and taking out after the Zr, nb and Hf are completely smelted.
(2) Adding the pre-melted Zr-Hf-Nb and the rest raw materials into an electric arc melting furnace, melting for 4-5 times, cooling to room temperature after metal is uniformly melted, and taking out a material block.
(3) And (5) polishing the material blocks to clean surface oxides.
(4) And (3) intercepting proper raw materials, carrying out vacuum induction copper die casting, and preparing alloy bars with diameters of 4mm and 5mm by adopting a copper die.
Comparative example 1
The composition of the zirconium-based amorphous alloy prepared in this comparative example was: zr 55 Cu 30 Ni 5 Al 10
The preparation method comprises the following steps:
(1) Weighing the components in proportion, adding the raw materials into a crucible, putting the crucible into a vacuum smelting furnace, vacuumizing to below 20Pa, washing gas twice, and turning on an induction smelting power supply to heat to 1900-2000 ℃ for smelting;
(2) And (3) cooling after the metal is completely melted, and when the temperature is reduced to 1200-1300 ℃, casting and cooling to room temperature in a mold with a regular shape.
(3) And (3) intercepting proper raw materials, carrying out vacuum induction copper die casting, and preparing an alloy bar with the diameter of 3mm by using a copper die.
As shown in FIGS. 1 to 3, XRD tests of the alloy bars of examples 1 to 7 and comparative example 1 showed diffuse scattering peaks, which correspond to the different angle reflections caused by the random crystal arrangement of the amorphous alloy, and thus, the 5mm bars of examples 1 to 7 of the present invention were all amorphous alloys.
As shown in FIGS. 4 to 6, stress-strain curve tests were performed on the alloy rods of examples 1 to 7 and comparative example 1, and it can be seen that the highest compressive strength of 1907MPa was exhibited in example 6 containing Nb, ti and Hf, followed by example 7, and that example 6 and example 7 exhibited stronger plasticity performance due to the simultaneous inclusion of Nb, ti and Hf.
The alloy bars of examples 1 to 7 and comparative example 1 were subjected to the compressive strength and hardness tests, and the results are shown in table 1 below.
TABLE 1
It can be seen that all the examples of the present document, while having plasticity not possessed by comparative example 1, also have hardness much higher than that of comparative example 1, providing a suitable solution to the technical problem.
In conclusion, the high-hardness large-size zirconium-based amorphous alloy with plastic deformation and the preparation method thereof utilize the characteristic that the rare earth element preferentially reacts with the oxygen element, and the damage of the oxygen element to the amorphous forming capability is not needed to be worried about by adopting industrial raw materials; the joint addition of Nb, ti and Hf also increases the configuration entropy and the mixed entropy of the system, and forms strong clusters in the Zr-Cu-Ni-Al-Ti system, thereby causing the uneven distribution of free volume, and improving the plasticity and hardness of the material while increasing the forming capability of the amorphous alloy.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (8)
1. A high-hardness large-size zirconium-based amorphous alloy with plastic deformation is characterized in that the atomic percent expression is as follows:
Zr a Cu b Ni c Al d Ti e Nb f Hf g M r (ii) a Wherein
a+b+c+d+e+f+g+r＝100；
M is a rare earth element; and
50＜a＜65；
10＜b＜20；
5＜c＜15；
5＜d＜15；
0≤e＜10；
0≤f＜10；
0＜g＜2；
0＜r＜0.5。
2. large-size zirconium based amorphous alloy with high hardness and plastic deformation according to claim 1 wherein,
the M comprises Y, dy, lu, ho, yb, ce and Rh.
3. Large-size zirconium based amorphous alloy with high hardness and plastic deformation according to claim 1 wherein,
the amorphous forming ability of the high-hardness large-size zirconium-based amorphous alloy with plastic deformation is not less than 5mm.
4. Large-size zirconium based amorphous alloy with high hardness and plastic deformation according to claim 1 wherein,
the compressive strength of the high-hardness large-size zirconium-based amorphous alloy with plastic deformation is not less than 1600MPa.
5. A large-size zirconium-based amorphous alloy with high hardness and plastic deformation according to claim 1, wherein,
the hardness Hv 0.5 of the high-hardness large-size zirconium-based amorphous alloy with plastic deformation is not less than 580.
6. Large-size zirconium based amorphous alloy with high hardness and plastic deformation according to claim 1 wherein,
the plastic elongation of the high-hardness large-size zirconium-based amorphous alloy with plastic deformation is not less than 4%.
7. A preparation method of a high-hardness large-size zirconium-based amorphous alloy with plastic deformation is characterized by comprising the following steps:
step S1, converting the components into mass ratios according to the atomic percentages in claim 1, and weighing and preparing the raw materials;
s2, performing electric arc premelting on the refractory metal, hf and part of Zr to obtain a premelted material;
s3, performing vacuum induction melting on the pre-melted material and the other raw materials for 4-5 times until the materials are uniformly melted, and taking out the materials after the materials are completely cooled to obtain a material block;
and S4, polishing the material block, and then die-casting the material block in a vacuum induction copper mold to obtain the high-hardness large-size zirconium-based amorphous alloy with plastic deformation.
8. The method according to claim 7,
the vacuum induction melting in the step S3 comprises the following steps:
vacuum degree not greater than 10 -1 MPa；
The protective gas comprises Ar and N 2 。
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| CN102965599A (en) * | 2012-11-26 | 2013-03-13 | 华为技术有限公司 | Zirconium-based amorphous alloy |
| CN103695814A (en) * | 2012-12-31 | 2014-04-02 | 比亚迪股份有限公司 | Zirconium based amorphous alloy and preparation method thereof |
| CN103484800A (en) * | 2013-09-10 | 2014-01-01 | 黄利敏 | Zirconium-based amorphous alloy and preparation method thereof |
| CN107541682A (en) * | 2016-06-29 | 2018-01-05 | 比亚迪股份有限公司 | A kind of spring and preparation method thereof and for preparing its die assembly |
| WO2018107830A1 (en) * | 2016-12-12 | 2018-06-21 | 北京科技大学 | Highly plastic zirconium-based bulk amorphous alloy with no beryllium or nickel, and method for preparing same |
| CN106947925A (en) * | 2017-03-22 | 2017-07-14 | 中国科学院金属研究所 | A kind of Zr base block amorphous alloys and its preparation method and application |
| CN110923587A (en) * | 2019-12-20 | 2020-03-27 | 常州世竟液态金属有限公司 | Low-density titanium-based block amorphous alloy |
| CN114836700A (en) * | 2022-06-15 | 2022-08-02 | 盘星新型合金材料(常州)有限公司 | Large-size zirconium-based amorphous alloy with high strength and high hardness and preparation method thereof |
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