Zirconium-based bulk amorphous alloy with high thermal stability as well as preparation method and application of zirconium-based bulk amorphous alloy

Abstract

The invention discloses a zirconium-based bulk amorphous alloy with high thermal stability as well as a preparation method and application of the zirconium-based bulk amorphous alloy. The atomic expression of the zirconium-based bulk amorphous alloy with high thermal stability is ZraCubNicAldHfe, a, b, c, d and e are respectively atomic ratios of corresponding elements, and a is more than or equal to 45 and less than or equal to 50; 20 < = b < = 25; 10 < = c < = 15; 10 < = d < = 15; 5 < = e < = 10; and the sum of a, b, c, d and e is 100. The glass transition temperature and the crystallization temperature of the zirconium-based bulk amorphous alloy with the atomic expression are high, the glass transition temperature is larger than or equal to 460 DEG C, the crystallization temperature is larger than or equal to 538 DEG C, and the zirconium-based bulk amorphous alloy is high in thermal stability and not prone to crystallization in the post-processing process, so that the zirconium-based bulk amorphous alloy is suitable for a flexible gear of a harmonic reducer.

Description

Technical Field

[0001] The present invention relates to the technical field of harmonic deceleration materials, and in particular to a zirconium-based bulk amorphous alloy with high thermal stability, a preparation method and applications thereof. Background Art

[0002] A harmonic reducer is a transmission device that uses a wave generator to generate controllable elastic deformation waves in a flexspline, leveraging the interaction between the flexspline and a rigid pulley to achieve motion and power transmission. It consists of three core components: the rigid pulley, the flexspline, and the wave generator. Failure is often caused by fatigue fracture of the flexspline, necessitating optimization of the flexspline material.

[0003] Amorphous alloys (metallic glasses) are a new type of metallic material created by rapidly cooling liquid metal, preventing its atoms from nucleating, resulting in a structure with long-range disorder and short-range order. Compared to crystalline alloys of the same composition, amorphous alloys lack defects such as dislocations, grain boundaries, and stacking faults, resulting in exceptionally high strength, hardness, toughness, wear resistance, and corrosion resistance.

[0004] Among them, the width of the supercooled liquid phase zone of zirconium-based amorphous alloy materials is relatively large, and they exhibit good superplastic rheological properties in the supercooled temperature zone, making them suitable for manufacturing high-precision, complex-shaped micro components, such as the flexible wheel components of high-precision harmonic reducers. The post-processing process of zirconium-based amorphous flexible wheels will easily cause them to crystallize due to local temperature increases, which will eventually lead to a decrease in their performance. This is because the glass transition temperature of zirconium-based bulk amorphous alloys is around 400°C, and the crystallization temperature is around 460°C. Therefore, the glass transition temperature and crystallization temperature of zirconium-based bulk amorphous alloys are generally not high, resulting in poor thermal stability.

[0005] Therefore, in view of the shortcomings of the existing technology, it is necessary to provide a zirconium-based bulk amorphous alloy with high thermal stability, a preparation method and an application to solve the shortcomings of the existing technology. Summary of the Invention

[0006] The first object of the present invention is to avoid the shortcomings of the prior art and provide a zirconium-based bulk amorphous alloy with high thermal stability. The zirconium-based bulk amorphous alloy with high thermal stability has high glass transition temperature and crystallization temperature, thereby having high thermal stability.

[0007] The present invention provides a zirconium-based bulk amorphous alloy with high thermal stability, the atomic expression of which is: Zr a Cu b Ni c Al d Hf e ;

[0008] a, b, c, d, and e are the atomic ratios of the corresponding elements, where:

[0009] 45≤a≤50;

[0010] 20≤b≤25;

[0011] 10≤c≤15;

[0012] 10≤d≤15;

[0013] 5≤e≤10;

[0014] And the sum of a, b, c, d and e is 100.

[0015] The zirconium-based bulk amorphous alloy with high thermal stability is prepared from Zr, Cu, Ni, Al and Hf.

[0016] The high thermal stability zirconium-based bulk amorphous alloy of the present invention has the following atomic expression: Zr 45 Cu 25 Ni 11 Al 11 Hf8.

[0017] Preferably, the glass transition temperature of the zirconium-based bulk amorphous alloy is greater than or equal to 460°C.

[0018] Preferably, the crystallization temperature of the zirconium-based bulk amorphous alloy is greater than or equal to 538°C.

[0019] A second object of the present invention is to overcome the shortcomings of the prior art and provide a method for preparing a zirconium-based bulk amorphous alloy with high thermal stability. The zirconium-based bulk amorphous alloy obtained by this method has high glass transition temperature and crystallization temperature, thereby improving thermal stability.

[0020] The above-mentioned purpose of the present invention is achieved through the following technical measures:

[0021] A method for preparing the above-mentioned zirconium-based bulk amorphous alloy with high thermal stability is provided, comprising the following steps:

[0022] S1, adding Zr simple substance, CS1, Zr simple substance, Cu simple substance, Ni simple substance, Al simple substance and Hf simple substance according to the atomic percentage of the zirconium-based bulk amorphous alloy into a vacuum arc melting furnace equipment;

[0023] S2. In a vacuum arc melting furnace, the smelting raw materials of S1 are heated using a tungsten electrode, and multiple heating and cooling operations are performed to obtain an alloy ingot; and each heating and cooling operation is performed by heating to a temperature of 2235° C. to 2255° C. and maintaining the temperature for 5 to 10 minutes, stopping the heating and cooling the temperature for 5 to 20 minutes, and then washing the temperature with argon twice;

[0024] S3. The alloy ingot obtained in S2 is placed in a vacuum melting furnace as a raw material, and the alloy ingot is heated to 1200°C to 1300°C by a tungsten pole head. The melting time is 20s to 80s, and then the melt is injected into a mold. Finally, it is cooled for 10min to 20min, and the mold is taken out to obtain a zirconium-based bulk amorphous alloy of an amorphous rod.

[0025] Furthermore, the method for preparing the zirconium-based bulk amorphous alloy with high thermal stability of the present invention comprises the following steps:

[0026] S1. Adding Zr, Cu, Ni, Al and Hf into a vacuum arc melting furnace according to the atomic percentage of the zirconium-based bulk amorphous alloy;

[0027] S2. In a vacuum arc melting furnace, the smelting raw materials of S1 are heated using a tungsten electrode, and multiple heating and cooling operations are performed to obtain an alloy ingot; and each heating and cooling operation is performed by heating to a temperature of 2238° C. to 2245° C. and maintaining the temperature for 6 to 8 minutes, stopping heating and cooling for 10 to 15 minutes, and then washing the alloy ingot with argon gas twice.

[0028] S3. The alloy ingot obtained in S2 is placed in a vacuum melting furnace as a raw material, and the alloy ingot is heated to 1250°C to 1280°C by a tungsten pole head. The melting time is 30s to 60s, and then the melt is injected into a mold. Finally, it is cooled for 12min to 18min, and the mold is taken out to obtain a zirconium-based bulk amorphous alloy of an amorphous rod.

[0029] Furthermore, the method for preparing the zirconium-based bulk amorphous alloy with high thermal stability of the present invention comprises the following steps:

[0030] S1. Adding Zr, Cu, Ni, Al and Hf into a vacuum arc melting furnace according to the atomic percentage of the zirconium-based bulk amorphous alloy;

[0031] S2. In a vacuum arc melting furnace, the smelting raw materials of S1 are heated using a tungsten electrode, and multiple heating and cooling operations are performed to obtain an alloy ingot; and each heating and cooling operation is performed by heating to a temperature of 2240° C. and holding for 7 minutes, stopping heating and cooling for 13 minutes, and then washing with argon twice;

[0032] S3. The alloy ingot obtained in S2 is placed in a vacuum melting furnace as a raw material, and the alloy ingot is heated to 1268° C. by a tungsten pole head. The melting time is 40 seconds, and then the melt is injected into a mold. Finally, it is cooled for 15 minutes, and the mold is taken out to obtain a zirconium-based bulk amorphous alloy of an amorphous rod.

[0033] Before using the vacuum arc melting furnace equipment and the vacuum melting furnace, the oxygen content is tested using an oxygen content testing method. When the oxygen content is qualified, tungsten electrode head is used for heating.

[0034] The oxygen content test method is as follows: the vacuum degree is controlled at 3×10 -3 Pa, then introduce argon with a purity of ≥99.999wt%, strike an arc with the tungsten electrode, and then let the tungsten electrode absorb oxygen on the titanium ingot for 1min to 2min. When there is no oxidation phenomenon on the titanium ingot, the oxygen content is qualified.

[0035] A third object of the present invention is to provide a zirconium-based bulk amorphous alloy for use in a harmonic reducer, thereby overcoming the shortcomings of the prior art. The zirconium-based bulk amorphous alloy has high glass transition and crystallization temperatures, resulting in high thermal stability and is therefore suitable for use in a flexspline of a harmonic reducer.

[0036] The above-mentioned purpose of the present invention is achieved through the following technical measures:

[0037] Provided is an application of a zirconium-based bulk amorphous alloy in a harmonic reducer. The zirconium-based bulk amorphous alloy is prepared by the above-mentioned method for preparing a zirconium-based bulk amorphous alloy with high thermal stability.

[0038] The present invention provides a zirconium-based bulk amorphous alloy with high thermal stability, a preparation method and an application thereof, wherein the atomic expression of the zirconium-based bulk amorphous alloy with high thermal stability is: Zr a Cu b Ni c Al d Hf e ; a, b, c, d, e are the atomic ratios of the corresponding elements, respectively, wherein: 45≤a≤50; 20≤b≤25; 10≤c≤15; 10≤d≤15; 5≤e≤10; and the sum of a, b, c, d and e is 100. The glass transition temperature and crystallization temperature of the zirconium-based bulk amorphous alloy of the above atomic expression of the present invention are both high, wherein the glass transition temperature is greater than or equal to 460°C, and the crystallization temperature is greater than or equal to 538°C. The zirconium-based bulk amorphous alloy has high thermal stability and is not easily crystallized during post-processing, and is therefore suitable for the flexible pulley of the harmonic reducer. DETAILED DESCRIPTION

[0039] The technical solutions of the present invention are further illustrated with reference to the following examples. The experimental methods in the following examples, unless otherwise specified, are conventional methods. The raw materials, reagents, etc. used in the following examples, unless otherwise specified, can be purchased from conventional biochemical reagent stores or pharmaceutical companies. The purity of the Zr, Cu, Ni, Al, and Hf elements of the present invention is ≥99.9 wt%.

[0040] Example 1

[0041] A zirconium-based bulk amorphous alloy with high thermal stability, the atomic expression is: Zr a Cu b Ni c Al d Hf e .

[0042] a, b, c, d, and e are atomic ratios of corresponding elements, respectively, wherein: 45≤a≤50; 20≤b≤25; 10≤c≤15; 10≤d≤15; 5≤e≤10; and the sum of a, b, c, d, and e is 100.

[0043] The zirconium-based bulk amorphous alloy with high thermal stability is prepared from Zr, Cu, Ni, Al and Hf.

[0044] The method for preparing the zirconium-based bulk amorphous alloy with high thermal stability comprises the following steps:

[0045] S1. Adding Zr, Cu, Ni, Al and Hf into a vacuum arc melting furnace according to the atomic percentage of the zirconium-based bulk amorphous alloy;

[0046] S2. In a vacuum arc melting furnace, the smelting raw materials of S1 are heated using a tungsten electrode, and multiple heating and cooling operations are performed to obtain an alloy ingot; and each heating and cooling operation is performed by heating to a temperature of 2235° C. to 2255° C. and maintaining the temperature for 5 to 10 minutes, stopping the heating and cooling the temperature for 5 to 20 minutes, and then washing the temperature with argon twice;

[0047] S3. The alloy ingot obtained in S2 is placed in a vacuum melting furnace as a raw material, and the alloy ingot is heated to 1200°C to 1300°C by a tungsten pole head. The melting time is 20s to 80s, and then the melt is injected into a mold. Finally, it is cooled for 10min to 20min, and the mold is taken out to obtain a zirconium-based bulk amorphous alloy of an amorphous rod.

[0048] Before using vacuum arc melting furnace equipment and vacuum melting furnace, oxygen content is tested by oxygen content test method. When the oxygen content is qualified, tungsten electrode is used for heating. The oxygen content test method is: control the vacuum degree at 3×10 -3 Pa, then introduce argon gas with a purity of ≥99.999wt%, strike an arc with the tungsten electrode, and then let the tungsten electrode absorb oxygen on the titanium ingot for 1min to 2min. When there is no oxidation phenomenon on the titanium ingot, the oxygen content is qualified.

[0049] In the method for preparing a zirconium-based bulk amorphous alloy with high thermal stability of the present invention, the melting amount per smelting is controlled to be 75g to 85g. It should be noted that the titanium ingot in the present invention is a component commonly found in vacuum arc melting furnaces and vacuum melting furnaces, and the function of this titanium ingot is to absorb oxygen within the equipment. If the surface of the titanium ingot does not change color during smelting, it indicates that the oxygen content is low, i.e., the oxygen content is acceptable. The determination of the surface color of the titanium ingot is a method well known to those skilled in the art.

[0050] From a kinetic perspective, the zirconium-based bulk amorphous alloy of the present invention is a multi-component amorphous alloy with a more compact atomic structure, resulting in a more stable state. During solidification, crystal nucleation and growth are more strongly inhibited. Therefore, it is inferred that as the number of components increases, the amorphous alloy becomes more difficult to crystallize during rapid cooling, thereby exhibiting stronger glass-forming ability.

[0051] Moreover, when different elements in an alloy have significant differences in atomic radius, this difference helps the alloy atoms to be arranged more closely when stacked, increasing the density of atoms in an irregular and tight arrangement. This will result in a decrease in the energy change (i.e., enthalpy change ΔH) required for the alloy to transition between solid and liquid states, resulting in a lower Gibbs free energy for the alloy in the liquid state. In addition, if the atomic radius difference between alloying elements is large, it will also increase the viscosity of the alloy melt, thereby enhancing its ability to form an amorphous state. Furthermore, the large atomic size difference between elements will generate stress at the atomic scale, making the crystalline solid solution phase unstable, which is conducive to the formation of an amorphous structure in the alloy.

[0052] When the electronegativity of the constituent elements differs greatly, the strong attraction between them hinders the diffusion of atoms during solidification, resulting in an uneven distribution of chemical components at the atomic level. This unevenness is conducive to the formation of amorphous materials.

[0053] If there is a negative mixing enthalpy between the components, atomic clusters of multiple elements will form locally inside the alloy. These clusters promote the orderly arrangement of atoms within a short distance, but at the same time limit the diffusion of atoms over a long distance, making the formation of a crystalline phase difficult, thereby enhancing the alloy's ability to form an amorphous state.

[0054] The mixing enthalpy, atomic radius, electronegativity and density of each element in the zirconium-based bulk amorphous alloy of the present invention are shown in Table 1.

[0055] Table 1. Mixing enthalpy, atomic radius, electronegativity and density data of Zr, Al, Cu, Ni and Hf atoms

[0056]

[0057] Furthermore, the zirconium-based bulk amorphous alloys provided in subsequent examples of the present invention have also been shown to have high glass transition temperatures and crystallization temperatures, with the glass transition temperature being greater than or equal to 460°C and the crystallization temperature being greater than or equal to 538°C. Therefore, the zirconium-based bulk amorphous alloys of the present invention have high thermal stability, both in theory and in test data.

[0058] Example 2

[0059] A zirconium-based bulk amorphous alloy with high thermal stability, the other features of which are the same as those of Example 1, except that: a method for preparing the zirconium-based bulk amorphous alloy with high thermal stability comprises the following steps:

[0060] S1. Adding Zr, Cu, Ni, Al and Hf into a vacuum arc melting furnace according to the atomic percentage of the zirconium-based bulk amorphous alloy;

[0061] S2. In a vacuum arc melting furnace, the smelting raw materials of S1 are heated using a tungsten electrode, and multiple heating and cooling operations are performed to obtain an alloy ingot; and each heating and cooling operation is performed by heating to a temperature of 2238° C. to 2245° C. and maintaining the temperature for 6 to 8 minutes, stopping heating and cooling for 10 to 15 minutes, and then washing the alloy ingot with argon gas twice.

[0062] S3. The alloy ingot obtained in S2 is placed in a vacuum melting furnace as a raw material, and the alloy ingot is heated to 1250°C to 1280°C by a tungsten pole head. The melting time is 30s to 60s, and then the melt is injected into a mold. Finally, it is cooled for 12min to 18min, and the mold is taken out to obtain a zirconium-based bulk amorphous alloy of an amorphous rod.

[0063] Before using vacuum arc melting furnace equipment and vacuum melting furnace, oxygen content is tested by oxygen content test method. When the oxygen content is qualified, tungsten electrode is used for heating. The oxygen content test method is: control the vacuum degree at 3×10 -3 Pa, then introduce argon gas with a purity of ≥99.999wt%, strike an arc with the tungsten electrode, and then let the tungsten electrode absorb oxygen on the titanium ingot for 1min to 2min. When there is no oxidation phenomenon on the titanium ingot, the oxygen content is qualified.

[0064] Example 3

[0065] A zirconium-based bulk amorphous alloy with high thermal stability, the other characteristics of which are the same as those of Example 1, except that the atomic expression is: Zr 50 Cu 20 Ni 15 Al 10 Hf5.

[0066] The method for preparing the zirconium-based bulk amorphous alloy with high thermal stability comprises the following steps:

[0067] S1. Adding Zr, Cu, Ni, Al and Hf into a vacuum arc melting furnace according to the atomic percentage of the zirconium-based bulk amorphous alloy;

[0068] S2. In a vacuum arc melting furnace, the smelting raw materials of S1 are heated using a tungsten electrode, and multiple heating and cooling operations are performed to obtain an alloy ingot; and each heating and cooling operation is performed by heating to a temperature of 2235° C. and holding for 10 minutes, stopping heating and cooling for 5 minutes, and then washing with argon twice;

[0069] S3. The alloy ingot obtained in S2 is placed in a vacuum melting furnace as a raw material, and the alloy ingot is heated to 1200° C. by a tungsten pole head. The melt is poured into a mold for 20 seconds, and finally cooled for 20 minutes. The mold is removed to obtain a zirconium-based bulk amorphous alloy of an amorphous rod.

[0070] Before using vacuum arc melting furnace equipment and vacuum melting furnace, oxygen content is tested by oxygen content test method. When the oxygen content is qualified, tungsten electrode is used for heating. The oxygen content test method is: control the vacuum degree at 3×10 -3 Pa, then introduce argon with a purity of ≥99.999wt%, strike an arc with the tungsten electrode, and then let the tungsten electrode absorb oxygen on the titanium ingot for 1 minute. When there is no oxidation phenomenon on the titanium ingot, the oxygen content is qualified.

[0071] Example 4

[0072] A zirconium-based bulk amorphous alloy with high thermal stability, the other characteristics of which are the same as those of Example 1, except that the atomic expression is: Zr 45 Cu 25 Ni 10 Al 10 Hf 10 .

[0073] The method for preparing the zirconium-based bulk amorphous alloy with high thermal stability comprises the following steps:

[0074] S1. Adding Zr, Cu, Ni, Al and Hf into a vacuum arc melting furnace according to the atomic percentage of the zirconium-based bulk amorphous alloy;

[0075] S2. In a vacuum arc melting furnace, the smelting raw materials of S1 are heated using a tungsten electrode, and multiple heating and cooling operations are performed to obtain alloy ingots; and each heating and cooling operation is performed by heating to a temperature of 2255° C. and holding for 5 minutes, stopping heating and cooling for 20 minutes, and then washing with argon twice;

[0076] S3. The alloy ingot obtained in S2 is placed in a vacuum melting furnace as a raw material, and the alloy ingot is heated to 1300° C. by a tungsten pole head. The melting time is 80 seconds, and then the melt is injected into a mold. Finally, it is cooled for 10 minutes, and the mold is taken out to obtain a zirconium-based bulk amorphous alloy of an amorphous rod.

[0077] Before using vacuum arc melting furnace equipment and vacuum melting furnace, oxygen content is tested by oxygen content test method. When the oxygen content is qualified, tungsten electrode is used for heating. The oxygen content test method is: control the vacuum degree at 3×10 -3 Pa, then introduce argon with a purity of ≥99.999wt%, strike an arc with the tungsten electrode, and then let the tungsten electrode absorb oxygen on the titanium ingot for 2 minutes. When there is no oxidation phenomenon on the titanium ingot, the oxygen content is qualified.

[0078] Example 5

[0079] A zirconium-based bulk amorphous alloy with high thermal stability, the other characteristics of which are the same as those of Example 1, except that the atomic expression is: Zr 50 Cu 25 Ni 10 Al 10 Hf5.

[0080] The method for preparing the zirconium-based bulk amorphous alloy with high thermal stability comprises the following steps:

[0081] S1. Adding Zr, Cu, Ni, Al and Hf into a vacuum arc melting furnace according to the atomic percentage of the zirconium-based bulk amorphous alloy;

[0082] S2. In a vacuum arc melting furnace, the smelting raw materials of S1 are heated using a tungsten electrode, and multiple heating and cooling operations are performed to obtain an alloy ingot; and each heating and cooling operation is performed by heating to a temperature of 2238° C. and holding for 8 minutes, stopping heating and cooling for 15 minutes, and then washing with argon twice;

[0083] S3. The alloy ingot obtained in S2 is placed in a vacuum melting furnace as a raw material, and the alloy ingot is heated to 1250° C. by a tungsten pole head. The melting time is 60 seconds, and then the melt is injected into a mold. Finally, it is cooled for 12 minutes, and the mold is taken out to obtain a zirconium-based bulk amorphous alloy of an amorphous rod.

[0084] Before using vacuum arc melting furnace equipment and vacuum melting furnace, oxygen content is tested by oxygen content test method. When the oxygen content is qualified, tungsten electrode is used for heating. The oxygen content test method is: control the vacuum degree at 3×10 -3 Pa, then introduce argon with a purity of ≥99.999wt%, strike an arc with the tungsten electrode, and then let the tungsten electrode absorb oxygen on the titanium ingot for 2 minutes. When there is no oxidation phenomenon on the titanium ingot, the oxygen content is qualified.

[0085] Example 6

[0086] A zirconium-based bulk amorphous alloy with high thermal stability, the other characteristics of which are the same as those of Example 1, except that the atomic expression is: Zr 50 Cu 21 Ni 12 Al 12 Hf5.

[0087] The method for preparing the zirconium-based bulk amorphous alloy with high thermal stability comprises the following steps:

[0088] S1. Adding Zr, Cu, Ni, Al and Hf into a vacuum arc melting furnace according to the atomic percentage of the zirconium-based bulk amorphous alloy;

[0089] S2. In a vacuum arc melting furnace, the smelting raw materials of S1 are heated using a tungsten electrode, and multiple heating and cooling operations are performed to obtain alloy ingots; and each heating and cooling operation is performed by heating to a temperature of 2245° C. and holding for 6 minutes, stopping heating and cooling for 10 minutes, and then washing with argon twice;

[0090] S3. The alloy ingot obtained in S2 is placed in a vacuum melting furnace as a raw material, and the alloy ingot is heated to 1280° C. by a tungsten pole head. The melting time is 30 seconds, and then the melt is injected into a mold. Finally, it is cooled for 18 minutes, and the mold is taken out to obtain a zirconium-based bulk amorphous alloy of an amorphous rod.

[0091] Before using vacuum arc melting furnace equipment and vacuum melting furnace, oxygen content is tested by oxygen content test method. When the oxygen content is qualified, tungsten electrode is used for heating. The oxygen content test method is: control the vacuum degree at 3×10 -3 Pa, then introduce argon with a purity of ≥99.999wt%, strike an arc with the tungsten electrode, and then let the tungsten electrode absorb oxygen on the titanium ingot for 2 minutes. When there is no oxidation phenomenon on the titanium ingot, the oxygen content is qualified.

[0092] Example 7

[0093] A zirconium-based bulk amorphous alloy with high thermal stability, the other characteristics of which are the same as those of Example 1, except that the atomic expression is: Zr 45 Cu 20 Ni 10 Al 15 Hf 10 .

[0094] The method for preparing the zirconium-based bulk amorphous alloy with high thermal stability comprises the following steps:

[0095] S1. Adding Zr, Cu, Ni, Al and Hf into a vacuum arc melting furnace according to the atomic percentage of the zirconium-based bulk amorphous alloy;

[0096] S2. In a vacuum arc melting furnace, the smelting raw materials of S1 are heated using a tungsten electrode, and multiple heating and cooling operations are performed to obtain an alloy ingot; and each heating and cooling operation is performed by heating to a temperature of 2240° C. and holding for 7 minutes, stopping heating and cooling for 13 minutes, and then washing with argon twice;

[0097] S3. The alloy ingot obtained in S2 is placed in a vacuum melting furnace as a raw material, and the alloy ingot is heated to 1268° C. by a tungsten pole head. The melting time is 40 seconds, and then the melt is injected into a mold. Finally, it is cooled for 15 minutes, and the mold is taken out to obtain a zirconium-based bulk amorphous alloy of an amorphous rod.

[0098] Before using vacuum arc melting furnace equipment and vacuum melting furnace, oxygen content is tested by oxygen content test method. When the oxygen content is qualified, tungsten electrode is used for heating. The oxygen content test method is: control the vacuum degree at 3×10 -3 Pa, then introduce argon with a purity of ≥99.999wt%, strike an arc with the tungsten electrode, and then let the tungsten electrode absorb oxygen on the titanium ingot for 2 minutes. When there is no oxidation phenomenon on the titanium ingot, the oxygen content is qualified.

[0099] Example 8

[0100] A zirconium-based bulk amorphous alloy with high thermal stability, the difference is that the atomic expression is: Zr 50 Cu 20 Ni 13 Al 12 Hf5.

[0101] The preparation method of the zirconium-based bulk amorphous alloy with high thermal stability is the same as that of Example 7.

[0102] Example 9

[0103] A zirconium-based bulk amorphous alloy with high thermal stability, the atomic expression is: Zr 47.5 Cu 22.5 Ni 11 Al 12 Hf7.

[0104] The preparation method of the zirconium-based bulk amorphous alloy with high thermal stability is the same as that of Example 7.

[0105] Example 10

[0106] A zirconium-based bulk amorphous alloy with high thermal stability, the atomic expression is: Zr 48 Cu 22 Ni 11.5 Al 12.5 Hf6.

[0107] The preparation method of the zirconium-based bulk amorphous alloy with high thermal stability is the same as that of Example 7.

[0108] Example 11

[0109] A zirconium-based bulk amorphous alloy with high thermal stability, the atomic expression is: Zr 45 Cu 25 Ni 11 Al 11 Hf8.

[0110] The preparation method of the zirconium-based bulk amorphous alloy with high thermal stability is the same as that of Example 7.

[0111] Comparative Example 1

[0112] A zirconium-based bulk amorphous alloy with high thermal stability, the atomic expression is: Zr 55 Cu 23 Ni 10 Al 10 Hf2.

[0113] The preparation method of the zirconium-based bulk amorphous alloy with high thermal stability is the same as that of Example 7.

[0114] Comparative Example 2

[0115] A zirconium-based bulk amorphous alloy, the atomic expression is: Zr 40 Cu 28 Ni 16 Al 13 Hf3.

[0116] The preparation method of the zirconium-based bulk amorphous alloy is the same as that of Example 7.

[0117] Comparative Example 3

[0118] A zirconium-based bulk amorphous alloy, in which Mo atoms replace Hf atoms, and the atomic expression is: Zr 50 Cu 20 Ni 13 Al 12 Mo5.

[0119] The preparation method of the zirconium-based bulk amorphous alloy is the same as that of Example 7.

[0120] Comparative Example 4

[0121] A zirconium-based bulk amorphous alloy, in which Ta atoms replace Hf atoms, and the atomic expression is: Zr 50 Cu 20 Ni 13 Al 12 Ta5.

[0122] The preparation method of the zirconium-based bulk amorphous alloy is the same as that of Example 7.

[0123] Comparative Example 5

[0124] A zirconium-based bulk amorphous alloy with high thermal stability, the atomic expression is: Zr 50 Cu 25 Ni 14 Al 11 Hf0.

[0125] The preparation method of the zirconium-based bulk amorphous alloy is the same as that of Example 7.

[0126] Comparative Example 6

[0127] A zirconium-based bulk amorphous alloy, the atomic expression is: Zr 45 Cu 25 Ni 11 Al 11 Hf8.

[0128] The method for preparing the zirconium-based bulk amorphous alloy comprises the following steps:

[0129] S1. Adding Zr, Cu, Ni, Al and Hf into a vacuum arc melting furnace according to the atomic percentage of the zirconium-based bulk amorphous alloy;

[0130] S2. In a vacuum arc melting furnace, the smelting raw materials of S1 are heated using a tungsten electrode, and multiple heating and cooling operations are performed to obtain alloy ingots; and each heating and cooling operation is performed by heating to a temperature of 2228°C and maintaining it for 20 minutes, stopping heating and cooling it for 20 minutes, and then washing it with argon twice;

[0131] S3. The alloy ingot obtained in S2 is placed in a vacuum melting furnace as a raw material, and the alloy ingot is heated to 1268° C. by a tungsten pole head. The melting time is 80 seconds, and then the melt is injected into a mold. Finally, it is cooled for 20 minutes, and the mold is taken out to obtain a zirconium-based bulk amorphous alloy of an amorphous rod.

[0132] Before using the vacuum arc melting furnace equipment and the vacuum melting furnace, the oxygen content is tested using the oxygen content test method. When the oxygen content is qualified, the tungsten electrode head is used for heating. The oxygen content test method is: the vacuum degree is controlled at 3×10 - 3 Pa, then introduce argon with a purity of ≥99.999wt%, strike an arc with the tungsten electrode, and then let the tungsten electrode absorb oxygen on the titanium ingot for 2 minutes. When there is no oxidation phenomenon on the titanium ingot, the oxygen content is qualified.

[0133] Test Case

[0134] 1. Bulk amorphous alloy testing

[0135] The zirconium-based bulk amorphous alloys of Examples 3 to 11 and the zirconium-based bulk amorphous alloys of Comparative Examples 1 to 6 were subjected to bulk amorphous alloy testing. Specifically, a sample with a thickness of 3 mm and parallel upper and lower surfaces was cut out of the zirconium-based bulk amorphous alloy, the test surface was polished to a mirror effect, and then tested using an X-ray diffractometer. The test conditions were a scanning range of 20° to 100° and a scanning speed of 5° / min. The obtained data are shown in Table 2.

[0136] 2. Glass transition temperature test

[0137] The glass transition temperature of the zirconium-based bulk amorphous alloys of Examples 3 to 11 and the zirconium-based bulk amorphous alloys of Comparative Examples 1 to 6 were tested. Specifically, 10 mg small discs were cut from the zirconium-based bulk amorphous alloy, ultrasonically cleaned and blown dry, and then placed in a crucible of a differential scanning calorimeter. The test was carried out at a heating rate of 20 K / min from room temperature to 600°C. The obtained data are shown in Table 2.

[0138] 3. Crystallization temperature test

[0139] The zirconium-based bulk amorphous alloys of Examples 3 to 11 and the zirconium-based bulk amorphous alloys of Comparative Examples 1 to 6 were subjected to crystallization temperature tests. Specifically, 10 mg small discs were cut from the zirconium-based bulk amorphous alloys, ultrasonically cleaned and blown dry, and then placed in a crucible of a differential scanning calorimeter. The test was carried out at a heating rate of 20 K / min from room temperature to 600°C. The obtained data are shown in Table 2.

[0140] Table 2. Glass forming ability and tensile strength data of zirconium-based bulk amorphous alloys

[0141] Is it a bulk amorphous alloy? Glass transition temperature / ℃ Crystallization temperature / ℃ Example 3 yes 460 543 Example 4 yes 459 540 Example 5 yes 461 543 Example 6 yes 463 549 Example 7 yes 459 539 Example 8 yes 460 544 Example 9 yes 458 538 Example 10 yes 463 546 Example 11 yes 465 553 Comparative Example 1 no / / Comparative Example 2 no / / Comparative Example 3 no / / Comparative Example 4 no / / Comparative Example 5 yes 404 457 Comparative Example 6 no / /

[0142] It can be seen from the data in Table 2 that, by comparing Examples 3 to 11 with Comparative Examples 1 to 5, only when Zr atoms, Cu atoms, Ni atoms, Al atoms and Hf atoms are present at the same time and the atomic ratio is within the scope of the present invention, can a bulk amorphous alloy be formed, and can the glass transition temperature be greater than or equal to 460°C, and the crystallization temperature be greater than or equal to 538°C. It can be seen from Example 8 and Comparative Examples 3 and 4 that when the Hf atoms of the present invention are replaced by Mo atoms or Ta atoms, the bulk amorphous alloy of the present invention cannot be formed. The atomic species and atomic ratio of the zirconium-based bulk amorphous alloy of the present invention make the number of components, electronegativity difference, atomic radius difference and mixing enthalpy within the optimal range, creating favorable conditions for the formation of bulk amorphous alloys. The glass transition temperature of the zirconium-based bulk amorphous alloy of the present invention is greater than or equal to 460°C, and the crystallization temperature is greater than or equal to 538°C, so the zirconium-based bulk amorphous alloy has high thermal stability. Moreover, the atomic expression of the zirconium-based bulk amorphous alloy of Example 11 is Zr45 Cu 25 Ni 11 Al 11 When Hf8 is used, its glass transition temperature can reach up to 465℃, and its crystallization temperature can reach up to 553℃.

[0143] Example 12

[0144] A zirconium-based bulk amorphous alloy is used in a harmonic reducer. The zirconium-based bulk amorphous alloy is prepared by any one of the methods for preparing a zirconium-based bulk amorphous alloy with high thermal stability described in Examples 3 to 11.

[0145] It can be seen from the above-mentioned effect examples that the glass transition temperature of the zirconium-based bulk amorphous alloy of the present invention is greater than or equal to 460°C, and the crystallization temperature is greater than or equal to 538°C. Therefore, the zirconium-based bulk amorphous alloy has high thermal stability and is not easily crystallized during post-processing, so it can be used in flexible wheel products.

[0146] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A zirconium-based bulk amorphous alloy with high thermal stability, characterized in that: The atomic expression is: Zr a Cu b Ni c Al d Hf e ; a, b, c, d, and e are the atomic ratios of the corresponding elements, where: 45≤a≤50； 20≤b≤25； 10≤c≤15； 10≤d≤15； 5≤e≤10； And the sum of a, b, c, d and e is 100.

2. The zirconium-based bulk amorphous alloy with high thermal stability according to claim 1, characterized in that: It is prepared from Zr, Cu, Ni, Al and Hf.

3. The zirconium-based bulk amorphous alloy with high thermal stability according to claim 1, characterized in that: The atomic expression is: Zr 45 Cu 25 Ni 11 Al 11 Hf8.

4. The zirconium-based bulk amorphous alloy with high thermal stability according to claim 1, characterized in that: The glass transition temperature of the zirconium-based bulk amorphous alloy is greater than or equal to 460°C.

5. The zirconium-based bulk amorphous alloy with high thermal stability according to claim 1, characterized in that: The crystallization temperature of the zirconium-based bulk amorphous alloy is greater than or equal to 538°C.

6. A method for preparing a zirconium-based bulk amorphous alloy with high thermal stability according to any one of claims 2 to 5, characterized in that: The following steps are involved: S1. Adding Zr, Cu, Ni, Al and Hf into a vacuum arc melting furnace according to the atomic percentage of the zirconium-based bulk amorphous alloy; S2. In a vacuum arc melting furnace, the smelting raw materials of S1 are heated using a tungsten electrode, and multiple heating and cooling operations are performed to obtain an alloy ingot; and each heating and cooling operation is performed by heating to a temperature of 2235° C. to 2255° C. and maintaining the temperature for 5 to 10 minutes, stopping the heating and cooling the temperature for 5 to 20 minutes, and then washing the temperature with argon twice; S3. The alloy ingot obtained in S2 is placed in a vacuum melting furnace as a raw material, and the alloy ingot is heated to 1200°C to 1300°C by a tungsten pole head. The melting time is 20s to 80s, and then the melt is injected into a mold. Finally, it is cooled for 10min to 20min, and the mold is taken out to obtain a zirconium-based bulk amorphous alloy of an amorphous rod.

7. The method for preparing a zirconium-based bulk amorphous alloy with high thermal stability according to claim 6, wherein: The following steps are involved: S1. Adding Zr, Cu, Ni, Al and Hf into a vacuum arc melting furnace according to the atomic percentage of the zirconium-based bulk amorphous alloy; S2. In a vacuum arc melting furnace, the smelting raw materials of S1 are heated using a tungsten electrode, and multiple heating and cooling operations are performed to obtain an alloy ingot; and each heating and cooling operation is performed by heating to a temperature of 2238° C. to 2245° C. and maintaining the temperature for 6 to 8 minutes, stopping heating and cooling for 10 to 15 minutes, and then washing the alloy ingot with argon gas twice. S3. The alloy ingot obtained in S2 is placed in a vacuum melting furnace as a raw material, and the alloy ingot is heated to 1250°C to 1280°C by a tungsten pole head. The melting time is 30s to 60s, and then the melt is injected into a mold. Finally, it is cooled for 12min to 18min, and the mold is taken out to obtain a zirconium-based bulk amorphous alloy of an amorphous rod.

8. The method for preparing a zirconium-based bulk amorphous alloy with high thermal stability according to claim 7, characterized in that: The following steps are involved: S1. Adding Zr, Cu, Ni, Al and Hf into a vacuum arc melting furnace according to the atomic percentage of the zirconium-based bulk amorphous alloy; S2. In a vacuum arc melting furnace, the smelting raw materials of S1 are heated using a tungsten electrode, and multiple heating and cooling operations are performed to obtain an alloy ingot; and each heating and cooling operation is performed by heating to a temperature of 2240° C. and holding for 7 minutes, stopping heating and cooling for 13 minutes, and then washing with argon twice; S3. The alloy ingot obtained in S2 is placed in a vacuum melting furnace as a raw material, and the alloy ingot is heated to 1268° C. by a tungsten pole head. The melting time is 40 seconds, and then the melt is injected into a mold. Finally, it is cooled for 15 minutes, and the mold is taken out to obtain a zirconium-based bulk amorphous alloy of an amorphous rod.

9. The method for preparing a zirconium-based bulk amorphous alloy with high thermal stability according to any one of claims 6 to 8, characterized in that: Before using the vacuum arc melting furnace equipment and the vacuum melting furnace, the oxygen content is tested using an oxygen content test method. When the oxygen content is qualified, the tungsten electrode is used for heating; The oxygen content test method is as follows: the vacuum degree is controlled at 3×10 -3 Pa, then introduce argon with a purity of ≥99.999wt%, strike an arc with the tungsten electrode, and then let the tungsten electrode absorb oxygen on the titanium ingot for 1min to 2min. When there is no oxidation phenomenon on the titanium ingot, the oxygen content is qualified.

10. Application of a zirconium-based bulk amorphous alloy in a harmonic reducer, characterized in that: The zirconium-based bulk amorphous alloy is prepared by the method for preparing a zirconium-based bulk amorphous alloy with high thermal stability according to any one of claims 7 to 9.

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