A tungsten-based high-temperature bulk amorphous alloy and a method for preparing the same

Abstract

The application discloses a tungsten-based high-temperature bulk amorphous alloy and a preparation method thereof. a Co b Ta c B d , a, b, c and d represent atomic percentage contents of corresponding chemical elements, a=34-50, b=30-48, c=5-10, d=12-20, and a+b+c+d=100 is met simultaneously. The tungsten-based high-temperature bulk amorphous alloy has high glass transition temperature and crystallization temperature, has strong amorphous forming capacity, can obtain a bulk material with a three-dimensional size of not less than 1 mm, and has excellent corrosion resistance, excellent high-temperature softening resistance and long-lasting wear resistance, and has great application prospects in extreme environments such as high temperatures.

Description

Technical Field

[0001] This invention belongs to the field of amorphous alloy materials technology, specifically relating to a tungsten-based high-temperature bulk amorphous alloy and its preparation method. Background Technology

[0002] Amorphous alloys are a new type of metastable metallic material with periodic defects in their atomic structure. Their chemical homogeneity and the absence of grain boundaries and dislocations endow them with excellent mechanical properties and good corrosion resistance. Their unique structure also endows amorphous alloys with unique physical and chemical properties, such as excellent catalytic activity and soft magnetic properties. Therefore, amorphous alloys have broad application prospects in military, civilian, nuclear, machinery manufacturing, and precision device fields.

[0003] Amorphous alloys exist in a metastable energy state thermodynamically. Above their crystallization temperature (or glass transition temperature), they rapidly undergo structural relaxation, transforming into periodic crystals and losing their superior properties. Therefore, the crystallization temperature determines the service life and operating temperature range of amorphous alloys. Most amorphous alloys crystallize below 500℃, making them unsuitable for long-term use and high-temperature operation, which is one of the main bottlenecks in the high-temperature application of amorphous alloys. Therefore, developing novel high-thermal-stability high-temperature amorphous alloys is key to solving this problem.

[0004] Patent application number 202210567138.4 discloses a high-entropy amorphous alloy with high thermal stability. Based on the multi-component characteristics and the high-entropy effect, it is rationally designed to increase its glass transition temperature to 660℃ and its service temperature to the mid-temperature range (>600℃). However, its formed size is very limited, only tens of micrometers, and its thermal stability still cannot meet its high-temperature application requirements (>700℃). Literature discloses an IrNiTa high-temperature amorphous alloy (Li, MX et al., 2019.569(7754):p.99-103), whose glass transition temperature exceeds 1000K, and whose compressive strength can reach 3.7GPa at a high temperature of 1040K (~770℃), with a three-dimensional formed size in the millimeter range. However, this high-temperature amorphous alloy contains a high specific gravity of the rare and precious metal Ir (>1000 RMB / g, wt.%>30%), resulting in high cost.

[0005] Therefore, in order to meet the requirements of safe and stable service and engineering applications of amorphous alloys at high temperatures, it is necessary to develop high-temperature amorphous alloys with glass transition temperatures exceeding 1000K, three-dimensional forming dimensions at the millimeter level, and low cost without precious metals. Summary of the Invention

[0006] In view of this, the purpose of the present invention is to provide a tungsten-based high-temperature bulk amorphous alloy and its preparation method. The tungsten-based high-temperature bulk amorphous alloy has a high glass transition temperature (>1050K) and excellent high-temperature softening resistance, while also having a strong amorphous forming ability. It can obtain bulk materials with a three-dimensional size of not less than 1 mm and does not contain precious metals.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] This invention provides a tungsten-based high-temperature bulk amorphous alloy, the chemical formula of which is: W a Co b Ta c B d a, b, c, and d represent the atomic percentage content of the corresponding chemical elements, where a = 34–50, b = 30–48, c = 5–10, and d = 12–20. At the same time, a + b + c + d = 100 must be satisfied.

[0009] As a preferred technical solution, a = 38, b = 41, c = 5, d = 16.

[0010] As a preferred technical solution, a = 40, b = 37, c = 5, d = 18.

[0011] As a preferred technical solution, a = 42, b = 35, c = 5, d = 18.

[0012] As a preferred technical solution, a = 44, b = 33, c = 5, d = 18.

[0013] As a preferred technical solution, a = 46, b = 31, c = 5, d = 18.

[0014] As a preferred technical solution, the tungsten-based high-temperature bulk amorphous alloy is composed of a single amorphous phase, and its critical amorphous formation diameter is ≥1mm.

[0015] As a preferred technical solution, the glass transition temperature of the tungsten-based high-temperature bulk amorphous alloy is 1060-1200K, and the crystallization temperature is 1100-1300K.

[0016] As a preferred technical solution, the tungsten-based high-temperature bulk amorphous alloy has a compressive strength of 4500–5600 MPa, a Vickers hardness of 1500–1700, and a corrosion current density of 6.48 × 10⁻⁶ in a 3.5 wt.% NaCl solution. -6 ~8.23×10 -6 A / cm 2 The Young's modulus is 230–340 GPa.

[0017] As a preferred technical solution, the tungsten-based high-temperature bulk amorphous alloy has a hardness of 12.3 GPa at 900℃ and a wear rate of 9.02 × 10⁻⁶ at 800℃. -6 mm 3 / Nm, the wear rate at room temperature is 3.11×10 -7 mm 3 / Nm.

[0018] This invention also provides a method for preparing the aforementioned tungsten-based high-temperature bulk amorphous alloy, comprising the following steps:

[0019] (1) Weigh and batch the materials according to the atomic percentage content of each element in the tungsten-based high-temperature bulk amorphous alloy;

[0020] (2) Place the raw materials weighed in step (1) into an electric arc furnace and melt them uniformly under low vacuum to obtain a master alloy ingot.

[0021] (3) The master alloy ingot obtained in step (2) is heated to liquid state and rapidly solidified and cooled by water-cooled copper mold suction casting to prepare tungsten-based high-temperature bulk amorphous alloy.

[0022] As a preferred technical solution, in step (2), uniform melting under low vacuum means evacuating the gas pressure inside the electric arc furnace to below 20 Pa, and then filling it with argon gas for direct melting.

[0023] The beneficial effects of this invention are as follows:

[0024] The tungsten-based high-temperature bulk amorphous alloy of the present invention uses tungsten metal, a low-cost refractory metal, as the main component element. By controlling the chemical composition and content, bulk materials with a three-dimensional size of not less than 1 mm can be obtained. It is the first tungsten-based high-temperature amorphous alloy with a three-dimensional size of millimeters.

[0025] Compared with the prior art, the advantages of the present invention are:

[0026] 1. The tungsten-based high-temperature bulk amorphous alloy obtained by the present invention is mainly composed of tungsten, the metal with the highest melting point. Therefore, the tungsten-based high-temperature bulk amorphous alloy exhibits high thermal stability, excellent high-temperature softening resistance and high-temperature wear resistance. Its crystallization temperature is not lower than 1100K, which is much higher than most amorphous alloys. The high thermal stability provides a guarantee for its high-temperature service.

[0027] 2. The tungsten-based high-temperature bulk amorphous alloy obtained by this invention can maintain a high hardness of 12 GPa at 900℃, which is several times that of conventional nickel-based and cobalt-based high-temperature alloys, and exhibits a hardness of 9.02 × 10⁻⁶ at 800℃. -6 mm 3 Extremely low wear rate of / Nm, 3.11×10 at room temperature.-7 mm 3 With a wear rate of / Nm, it exhibits durable wear resistance from room temperature to high temperature.

[0028] 3. This invention, based on the localized atomic structure characteristics of amorphous alloys, selects a quasi-crystalline phase design and extensively inherits an icosahedral structure into the material to form a stable amorphous structure, suppressing the precipitation of crystalline phases during liquid solidification. The addition of boron atoms effectively improves the packing density of the structure, increases geometric misalignment, and the strong chemical interaction between boron atoms and metal atoms reduces the system's free energy, hindering the formation of crystalline phases from both thermodynamic and kinetic perspectives. The alloying of tungsten (Ta) element effectively lowers the liquidus temperature and increases the mixing entropy of the system while maintaining high thermal stability. Ultimately, this tungsten-based high-temperature bulk amorphous alloy can form bulk materials with three-dimensional dimensions of not less than 1 mm, making it the first tungsten-based high-temperature amorphous alloy with millimeter-level three-dimensional dimensions that can be prepared using rapid quenching technology.

[0029] 4. The tungsten-based high-temperature bulk amorphous alloy obtained in this invention primarily consists of tungsten, a metallic material known for its high rigidity, high hardness, and high density. This tungsten-based high-temperature bulk amorphous alloy inherits these characteristics, exhibiting high rigidity. Simultaneously, the addition of a metalloid, boron, promotes the formation of interatomic covalent bonds, thereby improving the material's strength and hardness. Therefore, this tungsten-based high-temperature bulk amorphous alloy possesses a Young's modulus of not less than 220 GPa, a Vickers hardness of not less than 1500, a compressive strength of not less than 4500 MPa, and a density of not less than 13.9 g / cm³. 3 The high hardness, high density, and self-sharpening properties unique to amorphous alloys make this tungsten-based high-temperature bulk amorphous alloy a promising material for kinetic energy penetrators with excellent penetration performance.

[0030] 5. The tungsten-based high-temperature bulk amorphous alloy obtained in this invention has an amorphous structure, high chemical homogeneity, and is free of high-energy defects such as dislocations and grain boundaries. During corrosion, it mainly exhibits uniform corrosion and does not undergo highly destructive autogalvanic corrosion. Furthermore, tungsten itself is a corrosion-resistant element, and a well-formed and dense protective oxide film can rapidly form on the sample surface. This oxide film can hinder the corrosion of Cl ions, effectively suppressing highly destructive pitting corrosion. Ultimately, the corrosion current density of this tungsten-based high-temperature bulk amorphous alloy in simulated seawater is as low as 6.48 × 10⁻⁶. -6 A / cm 2 The pitting potential (relative to the calomel electrode) is as high as 5.14V, and the passivation range is as wide as 5.45V.

[0031] 6. The preparation method of the tungsten-based high-temperature bulk amorphous alloy of the present invention is simple, requiring only melting under low vacuum, without the need for the high vacuum and repeated gas washing process required by existing melting methods. Attached Figure Description

[0032] To make the objectives, technical solutions, and beneficial effects of this invention clearer, the following figures are provided for illustration:

[0033] Figure 1 The XRD patterns are for Examples 1, 2, 3, 4, and 5.

[0034] Figure 2 The thermal analysis curves are for Examples 1, 2, 3, 4, and 5.

[0035] Figure 3 The curve of Vickers hardness versus temperature is shown in Example 2.

[0036] Figure 4 The curve showing the wear rate as a function of temperature in Example 2 is shown.

[0037] Figure 5 The images show the nanoindentation load-displacement curves for Examples 1, 2, 3, and 4.

[0038] Figure 6 The figures are the room temperature compressive stress-strain curves for Examples 1, 2, 3, and 4.

[0039] Figure 7 The figures show the potentiodynamic polarization curves of Examples 1, 2, 3, and 4 in 3.5 wt.% NaCl solution.

[0040] Figure 8 This is a diagram showing the 2mm diameter sample from Example 5. Detailed Implementation

[0041] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments described are not intended to limit the present invention.

[0042] Example 1: Preparation of W 46 Co 31 Ta5B 18 High-temperature bulk amorphous alloys

[0043] (1) Ingredients: According to chemical formula W 46 Co 31 Ta5B 18 Accurately weigh the metal raw materials with a purity of not less than 99.9 wt.% and the boron element with a purity of 99 wt.%.

[0044] (2) Smelting: Place the raw materials prepared in the previous step into the induction arc furnace, evacuate the induction arc furnace to a low vacuum of 20Pa, and then fill it with argon. Under the protective atmosphere of argon, smelt the raw materials multiple times to obtain the master alloy ingot.

[0045] (3) Suction casting sample: The master alloy ingot is placed on the suction casting copper mold, melted into liquid under a high-purity argon atmosphere and then sucked into the copper mold. After cooling, a tungsten-based high-temperature bulk amorphous alloy with a diameter of 1 mm is taken out.

[0046] W 46 Co 31 Ta5B 18 Performance testing of high-temperature bulk amorphous alloys:

[0047] (a) The amorphous structure of the sample was characterized by X-ray diffraction, such as Figure 1 As shown, the prepared sample has a completely amorphous structure.

[0048] (b) The thermal stability of the sample was investigated using a differential calorimeter at a heating rate of 20 K / min. Figure 2 As shown, W 46 Co 31 Ta5B 18 The glass transition temperature of the high-temperature bulk amorphous alloy is 1197K, the crystallization temperature is 1256K, and the supercooled liquid phase width is 59K.

[0049] (c) The Young's modulus and nanohardness of the samples were studied using a nanoindenter, such as... Figure 5 As shown, W is calculated. 46 Co 31 Ta5B 18 The Young's modulus and nanohardness of the high-temperature bulk amorphous alloy are 324 GPa and 20.97 GPa, respectively.

[0050] (d) The room temperature mechanical strength and microVickers hardness of the samples were tested using a universal testing machine and a Vickers hardness tester, such as... Figure 6 As shown, W 46 Co 31 Ta5B 18 The room temperature mechanical strength and Vickers hardness of the high-temperature bulk amorphous alloy are 5248 MPa and 1684, respectively.

[0051] (e) The corrosion performance of the samples in 3.5 wt.% NaCl solution was studied using an electrochemical workstation. The selected reference electrode was a calomel electrode, and the counter electrode was a platinum electrode. Figure 7 As shown, W 46 Co 31 Ta5B 18 The self-corrosion current of high-temperature bulk amorphous alloy is 6.48 × 10⁻⁶. -6 A / cm 2 The pitting potential is 5.14V relative to the reference, and the passivation range width is 5.45V.

[0052] (f) W was measured using Archimedes' displacement method 46 Co31 Ta5B 18 The density of the high-temperature bulk amorphous alloy is 15.28 g / cm³. 3 .

[0053] Example 2: Preparation of W 44 Co 33 Ta5B 18 High-temperature bulk amorphous alloys

[0054] (1) Ingredients: According to chemical formula W 44 Co 33 Ta5B 18 Accurately weigh the metal raw materials with a purity of not less than 99.9 wt.% and the boron element with a purity of 99 wt.%.

[0055] (2) Smelting: Place the raw materials prepared in the previous step into the induction arc furnace, evacuate the induction arc furnace to a low vacuum of 20Pa, and then fill it with argon. Under the protective atmosphere of argon, smelt the raw materials multiple times to obtain the master alloy ingot.

[0056] (3) Suction casting sample: The master alloy ingot is placed on the suction casting copper mold, melted into liquid under a high-purity argon atmosphere and then sucked into the copper mold. After cooling, a tungsten-based high-temperature bulk amorphous alloy with a diameter of 1 mm is taken out.

[0057] W 44 Co 33 Ta5B 18 Performance testing of high-temperature bulk amorphous alloys:

[0058] (a) The amorphous structure of the sample was characterized by X-ray diffraction, such as Figure 1 As shown, the prepared sample has a completely amorphous structure.

[0059] (b) The thermal stability of the sample was investigated using a differential calorimeter at a heating rate of 20 K / min. Figure 2 As shown, W 44 Co 31 Ta5B 18 The glass transition temperature of the high-temperature bulk amorphous alloy is 1182K, the crystallization temperature is 1236K, and the supercooled liquid phase width is 54K.

[0060] (c) The Young's modulus and nanohardness of the samples were studied using a nanoindenter, such as... Figure 5 As shown, W is calculated. 44 Co 31 Ta5B 18 The Young's modulus and nanohardness of the high-temperature bulk amorphous alloy are 320 GPa and 21.03 GPa, respectively.

[0061] (d) The room temperature mechanical strength and microVickers hardness of the samples were tested using a universal testing machine and a Vickers hardness tester, such as... Figure 6 As shown, W 44 Co 31 Ta5B 18 The room temperature mechanical strength and Vickers hardness of the high-temperature bulk amorphous alloy are 4654 MPa and 1663, respectively.

[0062] (e) Using a high-temperature hardness tester to study the change of microhardness of the sample with temperature, such as... Figure 3 As shown, it maintains a high hardness of approximately 12 GPa at a high temperature of 900℃.

[0063] (f) The wear rate of the samples under different temperatures in an atmospheric environment was studied using a high-temperature tribometer. A reciprocating wear method was adopted, with a 6mm alumina ball as the wear pair, a load of 5N, a wear time of 30min, a frequency of 2Hz, and a slip length of 10mm. The results are as follows: Figure 4 As shown in Table 1.

[0064] (g) The corrosion performance of the samples in 3.5 wt.% NaCl solution was studied using an electrochemical workstation. The selected reference electrode was a calomel electrode, and the counter electrode was a platinum electrode. Figure 7 As shown, W 44 Co 31 Ta5B 18 The self-corrosion current of high-temperature bulk amorphous alloy is 8.23 ​​× 10⁻⁶. -6 A / cm 2 The pitting potential relative to the reference is 4.35V, and the passivation range width is 4.69V.

[0065] (h) W was measured using Archimedes' displacement method. 44 Co 33 Ta5B 18 The density of the high-temperature bulk amorphous alloy is 14.98 g / cm³. 3 .

[0066] Table 1W 44 Co 31 Ta5B 18 Microhardness and wear rate of high-temperature bulk amorphous alloys at different temperatures

[0067]

[0068] Example 3: Preparation of W 42 Co 35 Ta5B 18 High-temperature bulk amorphous alloys

[0069] (1) Ingredients: According to chemical formula W 42 Co 35 Ta5B18 Accurately weigh the metal raw materials with a purity of not less than 99.9 wt.% and the boron element with a purity of 99 wt.%.

[0070] (2) Smelting: Place the raw materials prepared in the previous step into the induction arc furnace, evacuate the induction arc furnace to a low vacuum of 20Pa, and then fill it with argon. Under the protective atmosphere of argon, smelt the raw materials multiple times to obtain the master alloy ingot.

[0071] (3) Suction casting sample: The master alloy ingot is placed on the suction casting copper mold, melted into liquid under a high-purity argon atmosphere and then sucked into the copper mold. After cooling, the tungsten-based high-temperature bulk amorphous alloy with a diameter of 1.2 mm is taken out.

[0072] W 42 Co 35 Ta5B 18 Performance testing of high-temperature bulk amorphous alloys:

[0073] (a) The amorphous structure of the sample was characterized by X-ray diffraction, such as Figure 1 As shown, the prepared sample has a completely amorphous structure.

[0074] (b) The thermal stability of the sample was investigated using a differential calorimeter at a heating rate of 20 K / min. Figure 2 As shown, W 42 Co 35 Ta5B 18 The glass transition temperature of the high-temperature bulk amorphous alloy is 1168K, the crystallization temperature is 1212K, and the supercooled liquid phase width is 44K.

[0075] (c) The Young's modulus and nanohardness of the samples were studied using a nanoindenter, such as... Figure 5 As shown, W is calculated. 42 Co 35 Ta5B 18 The Young's modulus and nanohardness of the high-temperature bulk amorphous alloy are 303 GPa and 20.98 GPa, respectively.

[0076] (d) The room temperature mechanical strength and microVickers hardness of the samples were tested using a universal testing machine and a Vickers hardness tester, such as... Figure 6 As shown, W 42 Co 35 Ta5B 18 The room temperature mechanical strength and Vickers hardness of the high-temperature bulk amorphous alloy are 5544 MPa and 1643, respectively.

[0077] (e) The corrosion performance of the samples in 3.5 wt.% NaCl solution was studied using an electrochemical workstation. The selected reference electrode was a calomel electrode, and the counter electrode was a platinum electrode. Figure 7 As shown, W42 Co 31 Ta5B 18 The self-corrosion current of high-temperature bulk amorphous alloy is 7.23 × 10⁻⁶. -6 A / cm 2 The pitting potential relative to the reference is 4.27V, and the passivation range width is 4.61V.

[0078] (f) W was measured using Archimedes' displacement method 42 Co 35 Ta5B 18 The density of the high-temperature bulk amorphous alloy is 14.83 g / cm³. 3 .

[0079] Example 4: Preparation of W 40 Co 37 Ta5B 18 High-temperature bulk amorphous alloys

[0080] (1) Ingredients: According to chemical formula W 40 Co 37 Ta5B 18 Accurately weigh the metal raw materials with a purity of not less than 99.9 wt.% and the boron element with a purity of 99 wt.%.

[0081] (2) Smelting: Place the raw materials prepared in the previous step into the induction arc furnace, evacuate the induction arc furnace to a low vacuum of 20Pa, and then fill it with argon. Under the protective atmosphere of argon, smelt the raw materials multiple times to obtain the master alloy ingot.

[0082] (3) Suction casting sample: The master alloy ingot is placed on the suction casting copper mold, melted into liquid under a high-purity argon atmosphere and then sucked into the copper mold. After cooling, the tungsten-based high-temperature bulk amorphous alloy with a diameter of 1.2 mm is taken out.

[0083] W 40 Co 37 Ta5B 18 Performance testing of high-temperature bulk amorphous alloys:

[0084] (a) The amorphous structure of the sample was characterized by X-ray diffraction, such as Figure 1 As shown, the prepared sample has a completely amorphous structure.

[0085] (b) The thermal stability of the sample was investigated using a differential calorimeter at a heating rate of 20 K / min. Figure 2 As shown, W 40 Co 37 Ta5B 18 The glass transition temperature of the high-temperature bulk amorphous alloy is 1160K, the crystallization temperature is 1208K, and the supercooled liquid phase width is 48K.

[0086] (c) The Young's modulus and nanohardness of the samples were studied using a nanoindenter, such as... Figure 5 As shown, W is calculated. 40 Co 37 Ta5B 18 The Young's modulus and nanohardness of the high-temperature bulk amorphous alloy are 238 GPa and 17.83 GPa, respectively.

[0087] (d) The room temperature mechanical strength and microVickers hardness of the samples were tested using a universal testing machine and a Vickers hardness tester, such as... Figure 6 As shown, W 40 Co 37 Ta5B 18 The room temperature mechanical strength and Vickers hardness of the high-temperature bulk amorphous alloy are 5534 MPa and 1592, respectively.

[0088] (e) The corrosion performance of the samples in 3.5 wt.% NaCl solution was studied using an electrochemical workstation. The selected reference electrode was a calomel electrode, and the counter electrode was a platinum electrode. Figure 7 As shown, W 40 Co 37 Ta5B 18 The self-corrosion current of high-temperature bulk amorphous alloy is 7.15 × 10⁻⁶. -6 A / cm 2 The pitting potential relative to the reference is 4.13V, and the passivation range width is 4.47V.

[0089] (f) W was measured using Archimedes' displacement method 40 Co 37 Ta5B 18 The density of the high-temperature bulk amorphous alloy is 14.60 g / cm³. 3 .

[0090] Example 5: Preparation of W 38 Co 41 Ta5B 16 High-temperature bulk amorphous alloys

[0091] (1) Ingredients: According to chemical formula W 38 Co 41 Ta5B 16 Accurately weigh the metal raw materials with a purity of not less than 99.9 wt.% and the boron element with a purity of 99 wt.%.

[0092] (2) Smelting: Place the raw materials prepared in the previous step into the induction arc furnace, evacuate the induction arc furnace to a low vacuum of 20Pa, and then fill it with argon. Under the protective atmosphere of argon, smelt the raw materials multiple times to obtain the master alloy ingot.

[0093] (3) Suction casting sample: Place the master alloy ingot on the suction casting copper mold, melt it to a liquid state under a high-purity argon atmosphere, and then draw it into the copper mold. After cooling, take out a 2mm diameter tungsten-based high-temperature bulk amorphous alloy (such as...). Figure 8 (As shown).

[0094] W 38 Co 41 Ta5B 16 Performance testing of high-temperature bulk amorphous alloys:

[0095] (a) The amorphous structure of the sample was characterized by X-ray diffraction, such as Figure 1 As shown, the prepared sample has a completely amorphous structure.

[0096] (b) The thermal stability of the sample was investigated using a differential calorimeter at a heating rate of 20 K / min. Figure 2 As shown, W 38 Co 41 Ta5B 16 The glass transition temperature of the high-temperature bulk amorphous alloy is 1102K, the crystallization temperature is 1157K, and the supercooled liquid phase width is 55K.

[0097] (c) W was measured using the Archimedes displacement method. 38 Co 41 Ta5B 16 The density of the high-temperature bulk amorphous alloy is 14.22 g / cm³. 3 .

[0098] The above-described embodiments are merely preferred embodiments provided to fully illustrate the present invention, and the scope of protection of the present invention is not limited thereto. Equivalent substitutions or modifications made by those skilled in the art based on the present invention are all within the scope of protection of the present invention. The scope of protection of the present invention is defined by the claims.

Claims

1. A tungsten-based high temperature bulk amorphous alloy, characterized by: The chemical molecular formula of the tungsten-based high-temperature bulk amorphous alloy is: W a Co b Ta c B d a, b, c and d represent the atomic percentage content of the corresponding chemical elements, a=34-50, b=30-48, c=5-10, d=12-20, and a+b+c+d=100.

2. The tungsten-based, high-temperature bulk amorphous alloy of claim 1, wherein: a=38, b=41, c=5, d=16; or, a=40, b=37, c=5, d=18; or, a=42, b=35, c=5, d=18; or, a=44, b=33, c=5, d=18; or, a=46, b=31, c=5, d=18. a=38, b=41, c=5, d=16; or, a=40, b=37, c=5, d=18; or, a=42, b=35, c=5, d=18; or, a=44, b=33, c=5, d=18; or, a=46, b=31, c=5, d=18. a=38, b=41, c=5, d=16; or, a=40, b=37, c=5, d=18; or, a=42, b=35, c=5, d=18; or, a=44, b=33, c=5, d=18; or, a=46, b=31, c=5, d=18. The tungsten-based high-temperature bulk amorphous alloy is composed of a single amorphous phase, and the critical amorphous forming diameter is greater than or equal to 1 mm.

3. The tungsten-based high-temperature bulk amorphous alloy of claim 1 or 2, wherein: The glass transition temperature of the tungsten-based high-temperature bulk amorphous alloy is 1060-1200 K, and the crystallization temperature is 1100-1300 K.

4. The tungsten-based, high-temperature bulk amorphous alloy of claim 3, wherein: The method comprises the following steps:

5. The tungsten-based, high-temperature bulk amorphous alloy of claim 3, wherein: The compressive strength of the tungsten-based high-temperature bulk amorphous alloy is 4500-5600 MPa, the Vickers hardness is 1500-1700, the corrosion current density in 3.5 wt.% NaCl solution is 6.48*10 -6 ~8.23*10 -6 A / cm 2 , and the Young's modulus is 230-340 GPa.

6. The tungsten-based, high-temperature bulk amorphous alloy of claim 3, wherein: The tungsten-based high-temperature bulk amorphous alloy has a hardness of 12.3 GPa at 900 ℃, a wear rate of 9.02 x 10 -6 mm 3 / Nm at 800 ℃, and a wear rate of 3.11 x 10 -7 mm 3 / Nm at room temperature.

7. The method of producing a tungsten-based high-temperature bulk amorphous alloy according to any one of claims 1 to 6, characterized by: (1) The raw materials are weighed according to the nominal atomic proportion of the tungsten-based high-temperature bulk amorphous alloy; (2) The raw materials weighed in step (1) are placed in an electric arc furnace and uniformly melted under low vacuum to obtain a master alloy ingot; (3) The master alloy ingot obtained in step (2) is heated to a liquid state and rapidly solidified and cooled by water-cooled copper mold suction casting to prepare a tungsten-based high-temperature bulk amorphous alloy. In step (2), the uniform melting under low vacuum refers to vacuumizing the electric arc furnace to a gas pressure of less than or equal to 20 Pa, and then filling argon for direct melting.

8. The method of claim 7, wherein: ​

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