CN111996471B - Zirconium-based amorphous alloy and preparation method and application thereof - Google Patents

Zirconium-based amorphous alloy and preparation method and application thereof Download PDF

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CN111996471B
CN111996471B CN202010870326.5A CN202010870326A CN111996471B CN 111996471 B CN111996471 B CN 111996471B CN 202010870326 A CN202010870326 A CN 202010870326A CN 111996471 B CN111996471 B CN 111996471B
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马明臻
李博
齐浩男
张新宇
刘日平
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Abstract

The invention provides a zirconium-based amorphous alloy and a preparation method and application thereof, belonging to the technical field of amorphous alloys. Comprises the following elements: zirconium, aluminum, nickel, copper and cobalt, wherein the atomic number ratio of zirconium, aluminum, copper, nickel and cobalt is 55.7: 11.3: 28: x: y, wherein X + Y is 5 and X is not 0. In the invention, Zr55.7Al11.3Ni5Cu28The cobalt is used for replacing nickel in the alloy, so that the potential entropy of a system is increased, the amorphous forming capability of the zirconium-based amorphous alloy is improved, and the stability is improved. Meanwhile, the cobalt has good corrosion resistance and good biocompatibility with a human body, and if the cobalt is used for a biological implant material, the cobalt reduces toxic and side effects on the human body. In addition, the replacement of nickel element by cobalt changes Zr55.7Al11.3NiyCu28CoxThe bond energy of the combination among all metal atoms in the alloy system hinders the long-range diffusion of the atoms and improves the mechanical property of the zirconium-based amorphous alloy.

Description

Zirconium-based amorphous alloy and preparation method and application thereof
Technical Field
The invention relates to the technical field of amorphous alloys, in particular to a zirconium-based amorphous alloy and a preparation method and application thereof.
Background
Amorphous alloys (also known as metallic glasses) are novel alloy materials with long-range disorder and short-range order obtained by various modern rapid solidification metallurgical techniques. Bulk amorphous alloys, generally referred to as amorphous alloys having a critical diameter of more than 1 mm. The amorphous alloy has many excellent physical and chemical properties, such as high strength, high hardness, high elastic limit, high wear resistance, high corrosion resistance, superplasticity and the like, and has a very wide application prospect.
However, the existing amorphous alloy has the following technical problems: (1) because the structure of the amorphous alloy presents the characteristics of long-range disorder and short-range order, the amorphous alloy does not have plastic deformation mechanisms such as dislocation slip, twinning and work hardening when deformed like crystalline alloy, and particularly presents brittle fracture when stressed under the condition of room temperature, thereby causing limited room-temperature plastic deformation capability; (2) in the existing zirconium-based amorphous alloy system, all contain metallic nickel element, if the nickel-containing zirconium-based amorphous alloy is used for biomedical materials, because the nickel element can release nickel ions harmful to human bodies, the nickel element needs to be removed or reduced, so that the harm of the nickel element to the human bodies is eliminated or reduced.
Disclosure of Invention
In view of the above, the present invention provides a zirconium-based amorphous alloy, and a preparation method and an application thereof. The zirconium-based amorphous alloy provided by the invention partially replaces nickel element with cobalt, so that the harm of the nickel element to human body is reduced, and the zirconium-based amorphous alloy can be better used for biomedical materials; meanwhile, the zirconium-based amorphous alloy has excellent room temperature plastic deformation capacity.
The invention provides a zirconium-based amorphous alloy with a chemical formula of Zr55.7Al11.3NiyCu28CoxWherein X + Y is 5 and X is not 0.
Preferably, X is 1 and Y is 4.
Preferably, X is 2 and Y is 3.
Preferably, X is 3 and Y is 2.
Preferably, X is 4 and Y is 1.
Preferably, X is 5 and Y is 0.
The invention also provides a preparation method of the zirconium-based amorphous alloy in the technical scheme, which comprises the following steps:
preparing raw materials according to the element composition of the zirconium-based amorphous alloy in the technical scheme, and smelting the raw materials to obtain a master alloy ingot;
and carrying out suction casting on the master alloy ingot by using a water-cooling copper mold to obtain the zirconium-based amorphous alloy.
Preferably, the smelting is carried out in an argon atmosphere, and the pressure of the argon atmosphere is 0.4-0.5 MPa; the smelting is carried out in a non-consumable electric arc smelting furnace, the working current of the non-consumable electric arc smelting furnace is 300-500A, the smelting frequency is at least 4 times, and the smelting time is at least 60s each time.
Preferably, the cooling speed of the suction casting is at least 200 ℃/s, the water-cooled copper die is cylindrical, and the diameter of the cylinder is 4mm, 5mm, 6mm, 7mm or 8 mm.
The invention also provides the application of the zirconium-based amorphous alloy in the technical scheme or the zirconium-based amorphous alloy prepared by the preparation method in the technical scheme as a biomedical material.
The invention provides a zirconium-based amorphous alloy with a chemical formula of Zr55.7Al11.3NiyCu28CoxWherein X + Y is 5 and X is not 0. Cobalt and nickel are both elements of group VIII of the fourth period of the periodic Table of the elements, and have very similar physical and chemical properties; atomic radii of elements such as cobalt and nickel
Figure BDA0002650892030000021
Equal, comparable atomic weights, 58.93 and 58.69, respectively, and very close electronegativities, 1.88 and 1.91, respectively, provide feasibility for cobalt to replace nickel. From the thermodynamic point of view of the interactions between atoms, replacement of Zr by cobalt55.7Al11.3Ni5Cu28The nickel in the alloy increases the potential entropy of the system, improves the amorphous forming capability of the zirconium-based amorphous alloy and improves the stability of the zirconium-based amorphous alloy. Meanwhile, the cobalt has good corrosion resistance and good biocompatibility with a human body, and if the cobalt is used for a biological implant material, the cobalt reduces toxic and side effects on the human body. In addition, the replacement of nickel element by cobalt changes Zr55.7Al11.3NiyCu28CoxThe bond energy of the combination among all metal atoms in the alloy system hinders the long-range diffusion of the atoms and improves the mechanical property of the zirconium-based amorphous alloy. Therefore, the invention replaces Zr with cobalt element55.7Al11.3Ni5Cu28The nickel element in the amorphous alloy obtains the amorphous alloy with stronger amorphous forming capability, good thermal stability, excellent mechanical property and good corrosion resistance, and the obtained zirconium-based amorphous alloy has larger critical dimension.
Drawings
FIG. 1 is an example 1 ℃ >6 Zr obtained55.7Al11.3NiyCu28Cox(x ═ 0,1,2,3,4, and 5) zirconium-based amorphous alloys at 5 × 10-4s-1Room temperature compressive stress strain curve at strain rate;
FIG. 2 shows Zr in a predetermined size obtained in examples 1 to 655.7Al11.3NiyCu28Cox(x ═ 0,1,2,3,4, and 5) typical XRD diffraction patterns of the zirconium-based amorphous alloys.
Detailed Description
The invention provides a zirconium-based amorphous alloy with a chemical formula of Zr55.7Al11.3NiyCu28CoxWherein X + Y is 5 and X is not 0.
In the present invention, the zirconium-based amorphous alloy further contains inevitable impurities.
In the present invention, X + Y is 5; the X is preferably any number between 0 and 5.
In a specific embodiment of the present invention, X is 1, Y is 4, that is, the atomic number ratio of zirconium, aluminum, copper, nickel, and cobalt is 55.7: 11.3: 28: 4: 1; the shape of the zirconium-based amorphous alloy is preferably a cylinder, the critical diameter of the cylinder is 6mm, and the length of the cylinder is preferably more than or equal to 80 mm.
In a specific embodiment of the present invention, X is 2 and Y is 3, i.e., the atomic number ratio of zirconium, aluminum, copper, nickel, and cobalt is 55.7: 11.3: 28: 3: 2; the shape of the zirconium-based amorphous alloy is preferably a cylinder, the critical diameter of the cylinder is preferably 8mm, and the length of the cylinder is preferably more than or equal to 80 mm.
In a specific embodiment of the present invention, X is 3 and Y is 2, i.e., the atomic number ratio of zirconium, aluminum, copper, nickel, and cobalt is 55.7: 11.3: 28: 2: 3; the shape of the zirconium-based amorphous alloy is preferably a cylinder, the critical diameter of the cylinder is 6mm, and the length of the cylinder is preferably more than or equal to 80 mm.
In a specific embodiment of the present invention, X is 4, Y is 1, that is, the atomic number ratio of zirconium, aluminum, copper, nickel, and cobalt is 55.7: 11.3: 28: 1: 4; the shape of the zirconium-based amorphous alloy is preferably a cylinder, the critical diameter of the cylinder is 4mm, and the length of the cylinder is preferably more than or equal to 80 mm.
In a specific embodiment of the present invention, X is 5 and Y is 0, i.e., the atomic number ratio of zirconium, aluminum, copper, nickel and cobalt is 55.7: 11.3: 28: 0: 5; the shape of the zirconium-based amorphous alloy is preferably a cylinder, the critical diameter of the cylinder is 4mm, and the length of the cylinder is preferably more than or equal to 80 mm.
The invention uses cobalt to replace Zr55.7Al11.3Ni5Cu28The nickel in the alloy increases the potential entropy of the system and improves the amorphous forming capability and stability of the zirconium-based amorphous alloy. Meanwhile, the cobalt has good corrosion resistance and good biocompatibility with a human body, and if the cobalt is used for a biological implantation material, the cobalt reduces toxic and side effects on the human body. In addition, the cobalt replaces the nickel element, thereby changing Zr55.7Al11.3NiyCu28CoxBond energy combined among metal atoms in an alloy system hinders long-range diffusion of the atoms, and glass forming capacity, mechanical property, thermal stability and corrosion resistance of the amorphous alloy are improved, so that the final non-alloy has stronger amorphous forming capacity, large room temperature plastic deformation capacity and good thermal stability; and has a larger critical dimension.
The invention also provides a preparation method of the zirconium-based amorphous alloy in the technical scheme, which comprises the following steps:
preparing raw materials according to the element composition of the zirconium-based amorphous alloy in the technical scheme, and smelting the raw materials to obtain a master alloy ingot;
and carrying out suction casting on the master alloy ingot by using a water-cooling copper mold to obtain the zirconium-based amorphous alloy.
Preparing raw materials according to the element composition of the zirconium-based amorphous alloy in the technical scheme, and smelting the raw materials to obtain a master alloy ingot;
in the present invention, the mass purity of the raw material is preferably more than 99.9%, and the type of the raw material, that is, the form of addition of the element is not particularly limited as long as the element composition described in the above technical scheme can be satisfied. In the present invention, the melting is preferably performed in an argon atmosphere, and the pressure of the argon atmosphere is preferably 0.4 to 0.5MPa, more preferably 0.42 to 0.48MPa, and even more preferably 0.44 to 0.46 MPa. In the invention, the smelting is preferably carried out in a non-consumable arc smelting furnace, and the working current of the non-consumable arc smelting furnace is preferably 300-500A, more preferably 350-450A, and more preferably 400A; the number of times of melting is preferably at least 4 times, and more preferably 4 times; the melting time per melting is preferably at least 60 seconds, more preferably 60 seconds.
After obtaining the mother alloy ingot, the invention utilizes a water-cooling copper mold to carry out suction casting on the mother alloy ingot to obtain the zirconium-based amorphous alloy.
In the present invention, the cooling rate of the suction casting is preferably at least 200 ℃/s, and more preferably 200 ℃/s. In the present invention, the shape of the water-cooled copper mold is preferably a cylinder, and the diameter of the cylinder is preferably 4mm, 5mm, 6mm, 7mm or 8 mm.
In the invention, the preparation method of the zirconium-based amorphous alloy adopts a water-cooled copper mold suction casting mode for cooling, and utilizes the rapid cooling capacity of the water-cooled copper mold to evaluate Zr when nickel is replaced by different cobalt contents55.7Al11.3NiyCu28CoxThe amorphous forming ability and critical casting size of the alloy system; by changing the diameter of the cylindrical water-cooling copper mould, alloy cast rods with the diameters of 4mm, 5mm, 6mm, 7mm and 8mm can be obtained respectively, and the maximum critical dimension of the zirconium-based amorphous alloy with different cobalt contents can be obtained.
The invention also provides the application of the zirconium-based amorphous alloy in the technical scheme or the zirconium-based amorphous alloy prepared by the preparation method in the technical scheme as a biomedical material.
The following will explain the zirconium-based amorphous alloy and the preparation method and application thereof in detail with reference to the examples, but they should not be construed as limiting the scope of the invention.
Example 1
Preparation of Zr55.7Al11.3Ni5Cu28The method comprises the following specific steps:
high-purity filiform or granular metal materials with the purity of not less than 99.9 percent, such as zirconium, copper, iron and aluminum, are mixed according to a nominal component Zr55.7Al11.3Ni5Cu28Accurately balancing weight (ensuring error less than 0.5mg), and putting the prepared raw materials into a copper crucible of a non-consumable electric arc furnace;
the vacuum degree of the smelting furnace cavity is pumped to 6 multiplied by 10-3Below Pa, filling high-purity argon until the pressure of the cavity is 0.5MPa, and then smelting a titanium block to absorb residual oxygen elements in the environment;
under the protection of high-purity argon (99.999 percent), a non-consumable arc melting furnace (with the working current of 400A) is used for melting raw materials to obtain Zr as a component55.7Al11.3Ni5Cu28The master alloy ingot of (1); in order to make the composition of the master alloy uniform, each alloy ingot is overturned and remelted for 4 times, and the time for each smelting is 60 s.
Under the protection of argon atmosphere, Zr55.7Al11.3Ni5Cu28The melt is sucked into a water-cooled copper mould with excellent heat conduction capability, and the cooling speed of the water-cooled copper mould for suction casting is 200 ℃/s; by controlling the size of the water-cooled copper mould cavity, a series of rod-shaped zirconium-based amorphous alloys with the length of 60mm and the diameters of 4,5, 6, 7 and 8mm are obtained.
Example 2
Preparation of Zr55.7Al11.3Ni4Cu28Co1The preparation method was substantially the same as that of example 1, except that example 2 obtained a series of Zr lengths of 60mm and diameters of 4,5, 6, 7 and 8mm, respectively55.7Al11.3Ni4Cu28Co1A bar-shaped zirconium-based amorphous alloy.
Example 3
Preparation of Zr55.7Al11.3Ni3Cu28Co2The preparation method is substantially the same as that of example 1, except that example 3 obtains a series of Zr having a length of substantially 60mm and diameters of 4,5, 6, 7 and 8mm, respectively55.7Al11.3Ni3Cu28Co2A bar-shaped zirconium-based amorphous alloy.
Example 4
Preparation of Zr55.7Al11.3Ni2Cu28Co3The preparation method was substantially the same as that of example 1, except that example 4 obtained a series of Zr having a length of substantially 60mm and diameters of 4,5, 6, 7 and 8mm, respectively55.7Al11.3Ni2Cu28Co3A bar-shaped zirconium-based amorphous alloy.
Example 5
Preparation of Zr55.7Al11.3Ni1Cu28Co4The preparation method was substantially the same as that of example 1, except that example 5 obtained a series of Zr having a length of substantially 60mm and diameters of 4,5, 6, 7 and 8mm, respectively55.7Al11.3Ni1Cu28Co4A bar-shaped zirconium-based amorphous alloy.
Example 6
Preparation of Zr55.7Al11.3Cu28Co5The preparation method was substantially the same as that of example 1, except that example 6 obtained a series of Zr having a length of substantially 60mm and diameters of 4,5, 6, 7 and 8mm, respectively55.7Al11.3Cu28Co5A rod-shaped amorphous alloy.
The rod-shaped amorphous alloy with the diameter of 3mm and the length of 60mm obtained in examples 1 to 6 was processed into a rod-shaped amorphous alloy sample with the diameter of 3mm and the length of 6mm, the mechanical properties of the amorphous alloy were measured in the INSTRON-5982 universal testing machine, and the compressive strain rate was set to 5X 10-4s-1(ii) a To ensure reproducibility of the experimental data, 5 repeated compression tests were performed per example. Yield strength (. sigma.) of the amorphous alloys obtained in examples 1 to 6y) Elastic strain (σ)e) Fracture Strength (σ)f) Plastic strain (sigma)p) The results are shown in Table 1. The zirconium-based amorphous alloys obtained in examples 1 to 6 were 5X 10-4s-1The room temperature compressive stress strain curve at strain rate is shown in fig. 1.
TABLE 1 results of mechanical property test of amorphous alloys obtained in examples 1 to 6
Figure BDA0002650892030000061
As can be seen from fig. 1 and table 1: zr55.7Al11.3Ni5Cu28The amorphous alloy has strong elastic deformation capacity, and the deformation amount of the strain amount in the compression process is 3.54 percent, but the plastic deformation amount is very small and is only 0.27 percent. With the increase of the addition amount of Co element, the mechanical property of the zirconium-based amorphous alloy is greatly changed: when the content of Co is 1 at.%, the compressive overall strain is increased to 5.96 percent, the plastic deformation is increased to 1.76 percent, and the fracture strength is also increased from 1830MPa to 1913 MPa; when the Co content is 2 at.%, the overall performance of the zirconium-based amorphous alloy is optimal, the zirconium-based amorphous alloy is fractured when the compressive deformation stress of the alloy reaches 1742MPa, the yield of the zirconium-based amorphous alloy is realized, the compressive strain reaches 7.41 percent, and the stress reaches 1940 MPa; when the content of Co element is added to 3%, the plastic deformation amount, the compressive strain amount, etc. begin to decrease; the zirconium-based amorphous alloys containing Co in amounts of 3 at.%, 4 at.% and 5 at.% do not have plastic deformation and yield stages, and break after elastic deformation occurs directly. This shows that the mechanical properties of the zirconium-based amorphous alloy are improved and then reduced with the increase of the cobalt element content, i.e. the mechanical properties of the zirconium-based amorphous alloy can be optimized by adding a proper amount of cobalt element.
From the rod-shaped zirconium-based amorphous alloys having a diameter of 4mm and a length of 60mm obtained in examples 1 to 6, samples having a mass of 15mg (each sample was weighed with a balance having an accuracy of 10 ten-thousandth) were cut out, and characteristic thermophysical property parameters of each of the zirconium-based amorphous alloy samples were measured at a temperature increase rate of 10K/min by a Differential Scanning Calorimetry (DSC). The results are shown in Table 2.
TABLE 2 Zr55.7Al11.3Cu28NiyCox(x is 0,1,2,3,4,5, at%) characteristic thermophysical property parameter of the amorphous alloy at a temperature rise rate of 10K/min
Figure BDA0002650892030000071
In Table 2, TgIs the glass transition temperature, TxFor crystallization onset temperature, TpFor the crystallization peak temperature, TmIs the melting point temperature, T, of the amorphous alloylIs the liquidus temperature, Δ T, of the amorphous alloyxIs the width of supercooled liquid phase region, TrgIs about the glass transition temperature.
The activation energies of the amorphous alloys obtained in examples 1 to 6 corresponding to the characteristic temperatures were calculated by substituting the characteristic temperatures in Table 2 into the following Kissinger formula. For comparison, Zr used for calculation of activation energy55.7Al11.3Cu28NiyCox(x is 0,1,2,3,4,5, at%) the characteristic temperatures Tg, Tx, and Tp of the amorphous alloys, and the calculation results are shown in table 3:
Figure BDA0002650892030000072
wherein: phi is the rate of temperature rise and T is the characteristic temperature (glass transition temperature T)gCrystallization onset temperature TxCrystallization peak temperature Tp) E is the activation energy corresponding to each characteristic temperature, R is the ideal gas constant, and C is a constant.
TABLE 3 activation energy of zirconium-based amorphous alloys obtained in examples 1 to 6
Figure BDA0002650892030000073
Figure BDA0002650892030000081
In Table 3, EgActivation energy for atomic rearrangement for glass transition process; exNucleation activation energy for crystallization process; epIs the crystal nucleus growth activation energy in the crystallization process.
As can be seen from Table 3: e of zirconium-based amorphous alloy with increasing Co contentg、Ex、EpBoth show a tendency to increase first and then decrease, and both reach a maximum at a Co content of 2 at% or 3 at%. Shows that the addition of proper amount of cobalt atoms can greatly improve Zr55.7Al11.3Ni5Cu28The energy barrier of the crystallization process of the zirconium-based amorphous alloy hinders the crystallization process, namely, the zirconium-based amorphous alloy provided by the invention has higher thermal stability.
The zirconium-based amorphous alloys having a diameter of 3mm and a length of 60mm obtained in examples 1,2, 4 and 6 were treated to obtain zirconium-based amorphous alloy samples having a diameter of 3mm and a length of 4mm, and subjected to corrosion tests: the corrosion resistance of the zirconium-based amorphous alloy samples obtained in examples 1,2, 4 and 6 was tested using the electrochemical workstation of CHI660E, produced by shanghai chenghua: the zirconium-based amorphous alloy samples obtained in examples 1,2, 4 and 6 were used as cathodes, platinum electrodes were used as anodes, and the electrolytes were 0.6mol/L NaCl solution, 1mol/LHCl solution and 1mol/LH2SO4A solution; the measurement range of the potentiodynamic polarization curve is-1.5V-2.5V (relative to the reference electrode potential), and the scanning frequency is 0.001V/s. Test samples of the zirconium-based amorphous alloys obtained in examples 1,2, 4 and 6 at 0.6mol/LNaCl, 1mol/LHCl, 1mol/LH2SO4Potentiodynamic polarization curve parameters in solution, the results are shown in table 4.
TABLE 4 zeta potential polarization curve parameters of the samples of zirconium based amorphous alloys obtained in examples 1,2, 4 and 6
Figure BDA0002650892030000082
Figure BDA0002650892030000091
In Table 4, IcorrTo erode the current density, EcorrTo corrosion potential, EpitIs the pitting potential.
As can be seen from Table 4: zr provided by the invention55.7Al11.3NiyCu28Cox(x ═ 0,1, 3, 5 at.%) amorphous alloyAt a concentration of 0.6mol/LNaCl, 1mol/LHCl, 1mol/LH2SO4The polarization behavior in the three solutions is very similar, with increasing Co content, Zr55.7Al11.3NiyCu28CoxCorrosion current density of amorphous alloy in all solutions IcorrGradually decreases, the corrosion potential gradually increases, and the pitting potential E in NaCl solutionpitThe corrosion resistance of the zirconium-based amorphous alloy is further improved by adding Co.
FIG. 2 is a typical XRD diffraction pattern of the zirconium-based amorphous alloy with a certain size obtained in examples 1-6; from fig. 2, it can be derived: the critical dimension of the zirconium-based amorphous alloy is 6mm when the content of Co is 0 at.% and 1 at.%; when the content of Co element is increased to 2 at.%, the critical dimension is increased to 8 mm; the content of Co element is continuously increased, and the critical dimension of the zirconium-based amorphous alloy is in a trend of gradually reducing. According to the theory of amorphous formation, because Co element and Ni element have similar size effect, the influence on amorphous formation is small, and according to the theory of bit shape entropy of amorphous formation, a certain amount of Co element is added, so that the interaction among atoms is enhanced, diffusion is more difficult to occur, nucleation is not easy to occur, and the alloy of the system has higher amorphous formation capability.
The invention replaces the prior Zr by proper amount of cobalt element55.7Al11.3Ni5Cu28The nickel element in the amorphous alloy obtains the amorphous alloy with stronger amorphous forming capability, large room temperature plastic deformation capability and good thermal stability, and eliminates or reduces elements such as nickel atoms which are harmful to human bodies, thereby having larger application potential in the engineering field and the biological implantation material field.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (5)

1. A Zr-based amorphous alloy is characterized in that the chemical formula is Zr55.7Al11.3NiyCu28CoxWherein X + Y is 5, and X is more than 0 and less than or equal to 2.
2. A method for preparing the zirconium based amorphous alloy according to claim 1, comprising the steps of:
preparing raw materials according to the elemental composition of the zirconium-based amorphous alloy of claim 1, and smelting the raw materials to obtain a master alloy ingot;
and carrying out suction casting on the master alloy ingot by using a water-cooling copper mold to obtain the zirconium-based amorphous alloy.
3. The preparation method according to claim 2, wherein the smelting is performed under an argon atmosphere, and the pressure of the argon atmosphere is 0.4 to 0.5 MPa; the smelting is carried out in a non-consumable electric arc smelting furnace, the working current of the non-consumable electric arc smelting furnace is 300-500A, the smelting frequency is at least 4 times, and the smelting time is at least 60s each time.
4. The method according to claim 2, wherein the cooling rate of the suction casting is at least 200 ℃/s, and the water-cooled copper mold has a cylindrical shape having a diameter of 4mm, 5mm, 6mm, 7mm or 8 mm.
5. Use of the zirconium-based amorphous alloy according to claim 1 or the zirconium-based amorphous alloy prepared by the preparation method according to any one of claims 2 to 4 as a biomedical material.
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