A super wear-resistant high-temperature tungsten-based amorphous alloy and its preparation method

Abstract

The present invention discloses a super wear-resistant high temperature tungsten-based amorphous alloy and a preparation method thereof. The chemical formula of the super wear-resistant high temperature tungsten-based amorphous alloy is: W a Fe b B c C d , where a, b, c, and d represent the atomic percentage content of the corresponding chemical elements, a = 23 to 48, b = 32 to 57, c = 14 to 18, d = 2 to 6, and a + b + c + d = 100. The ultra-wear-resistant, high-temperature tungsten-based amorphous alloy is composed of a single amorphous phase. The ultra-wear-resistant, high-temperature tungsten-based amorphous alloy of the present invention has a glass transition temperature of up to 840°C and a crystallization temperature of approximately 900°C. It has good high-temperature stability and excellent amorphous forming ability. It can obtain bulk amorphous materials with a three-dimensional size of 1.5 to 2 mm and has a room temperature as low as 1.6×10 ‑7 mm 3 / Nm wear resistance, the high temperature tungsten-based amorphous alloy can also be prepared into powder, film, wire or strip and other forms and their combinations.

Description

Technical Field

[0001] The present invention belongs to the technical field of amorphous alloy materials, and in particular relates to an ultra-wear-resistant, high-temperature tungsten-based amorphous alloy and a preparation method thereof. Background Art

[0002] At present, metal materials are widely used in the fields of machinery manufacturing, aerospace, automobiles, ships, etc. However, during the service process, mechanical equipment will inevitably suffer from varying degrees of wear and tear, resulting in equipment failure, which makes wear resistance an important criterion for determining its service life. Therefore, it is particularly important to research and develop metal materials with excellent wear resistance. Amorphous alloys, with their unique structure of long-range disorder and short-range order, often have better strength, hardness, etc. than traditional alloy materials, which means that amorphous alloys often have better wear resistance. However, since amorphous alloys are in a metastable state in energy, the instantaneous high temperature generated during the wear process will cause the amorphous alloy to undergo local crystallization, thereby greatly weakening its wear resistance. At present, the glass transition temperature of most amorphous alloys does not exceed 700°C, and the crystallization temperature does not exceed 800°C, which undoubtedly poses a huge challenge to long-term service in the high temperature stage (above 700°C). Therefore, the development of high-temperature amorphous alloy systems with higher glass transition temperatures has become an urgent problem to be solved in this field.

[0003] Existing research shows that refractory metals with high melting points and high modulus, such as Ir and Ta, are ideal materials for designing high-temperature amorphous alloys. Amorphous alloys designed with them as the main components can have glass transition temperatures exceeding 700°C. For example, Ming-Xing Li et al. (Nature, 2019, 569 99-103) reported that IrNiTa(B) series high-temperature amorphous alloys with glass transition temperatures above 800°C and crystallization temperatures above 900°C exhibited extremely excellent wear resistance (Adv. Sci. 2023, 2301053). However, the manufacturing cost of this alloy is extremely high, making it difficult to apply in practice. Tungsten, as the metal material with the highest melting point, is much less expensive than Ir, Ta, etc., and is widely used in the manufacture of various high-temperature alloys and cemented carbides, showing excellent wear resistance. Unfortunately, due to tungsten's extremely high melting point, its crystallization driving force is high, resulting in limited glass-forming ability. Currently, only patent application number CN116926447 A discloses a WCoTaB refractory bulk amorphous alloy. However, this alloy still contains 5-10 at.% of the expensive metal Ta (~6000 ¥ / kg, 99.95 wt.%, Beijing Cuibolin Nonferrous Metals Technology Development Center Co., Ltd., October 2024). If a new tungsten-based amorphous alloy without any expensive metals and excellent glass-forming ability could be prepared, it would better meet service requirements and further expand its application range.

[0004] In summary, in order to further improve the wear resistance of the alloy and better serve in high-temperature extreme environments, it is very necessary to develop a tungsten-based amorphous alloy with excellent amorphous forming ability, high glass transition temperature and crystallization temperature, and ultra-high wear resistance. Summary of the Invention

[0005] The object of the present invention is to provide an ultra-wear-resistant high-temperature tungsten-based amorphous alloy and a preparation method thereof, which can have excellent amorphous forming ability, high glass transition temperature and crystallization temperature, and ultra-high wear resistance, and does not contain expensive metal elements.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] In the first aspect, the present invention provides a super wear-resistant high temperature tungsten-based amorphous alloy, the chemical formula of the super wear-resistant high temperature tungsten-based amorphous alloy is: a Fe b B c C d , wherein a, b, c, and d represent the atomic percentage content of the corresponding chemical elements, a=23-48, b=32-57, c=14-18, d=2-6, and a+b+c+d=100, and the ultra-wear-resistant high-temperature tungsten-based amorphous alloy is composed of a single amorphous phase.

[0008] Optionally, a=34-42, b=38-46, c=14-18, d=2-6, and a+b+c+d=100.

[0009] Optionally, the form of the ultra-wear-resistant and high-temperature tungsten-based amorphous alloy includes any one or a combination of two or more of powder, film, wire, strip and block.

[0010] Optionally, the block diameter of the ultra-wear-resistant and high-temperature tungsten-based amorphous alloy is greater than 1.5 mm.

[0011] Optionally, the block diameter of the ultra-wear-resistant and high-temperature tungsten-based amorphous alloy is greater than 2 mm.

[0012] Optionally, the ultra-wear-resistant high-temperature tungsten-based amorphous alloy has a glass transition temperature of 780-840°C and a crystallization temperature of 820-900°C.

[0013] Optionally, the ultra-wear-resistant high-temperature tungsten-based amorphous alloy has a room temperature compressive strength of 5 to 6 GPa, a Young's modulus of 240 to 300 GPa, and a microhardness of 1500 to 1700 HV.

[0014] Optionally, the room temperature friction coefficient of the ultra-wear-resistant high-temperature tungsten-based amorphous alloy is 0.28-0.37, and the room temperature wear rate is 1.6×10 -7 ~1.2×10 -6mm 3 / Nm.

[0015] In a second aspect, the present invention provides a method for preparing the aforementioned ultra-wear-resistant and high-temperature tungsten-based amorphous alloy, comprising at least one of sputtering, ball milling, atomization, belt spinning, suction casting or die casting.

[0016] Optionally, the following preparation steps are included:

[0017] S1. Weigh the raw materials according to the alloy composition: The chemical formula of the ultra-wear-resistant high-temperature tungsten-based amorphous alloy is: W a Fe b B c C d , wherein a, b, c, and d represent the atomic percentage content of the corresponding chemical elements, a=23-48, b=32-57, c=14-18, d=2-6, and a+b+c+d=100;

[0018] S2 raw material smelting to prepare a master alloy ingot: The raw material weighed in step S1 is uniformly smelted in a vacuum or protective atmosphere to prepare a master alloy ingot;

[0019] S3. Suction casting of the master alloy ingot into a water-cooled copper mold: The master alloy ingot prepared in step S2 is heated and smelted, and then suction cast into a water-cooled copper mold for cooling to prepare a high-temperature tungsten-based amorphous alloy.

[0020] In summary, the present invention has at least one of the following beneficial effects:

[0021] 1. The present invention provides an ultra-wear-resistant, high-temperature tungsten-based amorphous alloy. By adopting four specific elements, W, Fe, B and C, and a specific element ratio, a unique quaternary single-phase amorphous alloy is prepared. Its glass transition temperature is 780-840°C, and its crystallization temperature is 820-900°C. It has excellent high-temperature thermal stability. In addition, the present invention uses low-cost tungsten among refractory metals as the main component element and does not contain precious metal elements, which effectively reduces manufacturing costs. The prepared material has excellent amorphous forming ability and can prepare bulk materials with a diameter of 1.5 mm or even more than 2 mm. In addition, the good amorphous forming ability enables the amorphous alloy provided by the present invention to also prepare amorphous materials in the form of powders, films, wires or strips and their combinations.

[0022] 2. The present invention provides an ultra-wear-resistant, high-temperature tungsten-based amorphous alloy with excellent comprehensive properties, including high strength, stiffness, hardness, and excellent friction and wear resistance. In subsequent examples, the room-temperature compressive strength of the amorphous alloy was measured to be above 5 GPa, the Young's modulus to be nearly 300 GPa, and the microhardness to be 1650 HV. At room temperature, the friction coefficient is as low as 0.28, and the wear rate is as low as 1.6×10-7 mm 3 / Nm.

[0023] 3. The present invention provides a super wear-resistant high-temperature tungsten-based amorphous alloy, the chemical formula of which is: W a Fe b B c C d , where a, b, c, and d represent the atomic percentage content of the corresponding chemical elements, a=23~48, b=32~57, c=14~18, d=2~6, and a+b+c+d=100, bulk amorphous with a diameter of more than 1.5 mm can be formed within a wider composition range, indicating that it has excellent amorphous forming ability within a wider composition range. This series of alloys can provide a wide range of selection space and controllability for industrial applications; further, a=34~42, b=38~46, c=14~18, and d=2~6, bulk amorphous with a diameter of more than 2 mm can be formed within a wider composition range, indicating that it has even better amorphous forming ability within this wider composition range. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The XRD patterns of the samples of Examples 1-5 of the present invention are shown.

[0025] Figure 2 Neutron scattering diagrams of the samples of Examples 3 and 5 of the present invention.

[0026] Figure 3 These are the thermal analysis curves of the samples of Examples 3 and 5 of the present invention.

[0027] Figure 4 These are the stress-strain curves of the samples of Examples 3 and 5 of the present invention.

[0028] Figure 5 Nanoindentation load-displacement curves of the samples of Examples 3 and 5 of the present invention.

[0029] Figure 6 Microhardness diagrams of the samples of Examples 3 and 5 of the present invention.

[0030] Figure 7 Graph showing the coefficient of friction of Examples 3 and 5 of the present invention.

[0031] Figure 8 Graph showing the wear curves of Examples 3 and 5 of the present invention. DETAILED DESCRIPTION

[0032] The present invention provides an ultra-wear-resistant, high-temperature tungsten-based amorphous alloy and a method for preparing the same. To clarify the objectives, technical solutions, and effects of the present invention, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are intended only to illustrate the present invention and are not intended to limit the present invention.

[0033] The unique atomic arrangement of amorphous alloys with long-range disorder and short-range order determines that amorphous alloys have a series of unique properties, such as good corrosion resistance, high strength, good wear resistance, etc., which provides a potential basis for amorphous alloys to be used as new structural materials in special fields. Generally speaking, amorphous alloys with higher glass transition temperature and crystallization temperature have better room temperature and high temperature mechanical properties, such as Ir-based and Ta-based. However, the high cost of raw materials greatly limits the actual engineering application scope of these high-stability amorphous alloys. The inventor disclosed a high-temperature W in the previously applied Chinese invention 202310886995.5. a Co b Ta c B d An amorphous alloy and a preparation method thereof, wherein the alloy has a high glass transition temperature and crystallization temperature, and its thermal stability can meet the requirements of high-temperature (above 700°C) applications. At the same time, it has strong amorphous forming ability, and a bulk material with a three-dimensional size of not less than 1 mm can be obtained. However, the addition of the expensive metal element Ta is still unavoidable. In order to break through the cost limit of expensive metal elements, the inventors, after a long period of research, surprisingly found that the use of a quaternary alloy of W, Fe, B, and C in a specific ratio, the synergistic effect of the four elements makes the quaternary alloy system with a specific ratio have excellent amorphous forming ability, and can obtain a tungsten-based bulk amorphous material with a critical size of more than 1.5 mm in diameter, or even up to 2 mm. In addition, the prepared specific tungsten-based amorphous material has a glass transition temperature above 700°C, even above 780°C, and can reach a maximum of 840°C. It has excellent high-temperature stability and can meet the requirements of high-temperature (above 700°C) applications. The tungsten-based amorphous alloy has excellent wear resistance. The friction coefficient at room temperature can reach below 0.5, even below 0.37, and the lowest can reach 0.28. The wear rate at room temperature can reach 5×10 -6 mm 3 / Nm, even reaching 1.2×10 -6 mm 3 / Nm, the lowest can reach 1.6×10 -7 mm 3 / Nm. Thus, the W, Fe, B, and C quaternary alloy provided by the present invention combines excellent amorphous-forming ability, high glass transition temperature and crystallization temperature, and ultra-high wear resistance, while containing no expensive metal elements. The present invention is based on this research.

[0034] Specifically, in some embodiments of the present invention, a super wear-resistant and high temperature tungsten-based amorphous alloy is provided, and the chemical formula of the super wear-resistant and high temperature tungsten-based amorphous alloy is: W a Fe b B c C d , wherein a, b, c, and d represent the atomic percentage content of the corresponding chemical elements, a=23-48, b=32-57, c=14-18, d=2-6, and a+b+c+d=100, and the ultra-wear-resistant high-temperature tungsten-based amorphous alloy is composed of a single amorphous phase; preferably, a=34-42, b=38-46, c=14-18, d=2-6, and a+b+c+d=100; more preferably, a=36-40, b=40-44, c=14-18, d=2-6, and a+b+c+d=100.

[0035] In some embodiments of the present invention, the ultra-wear-resistant, high-temperature tungsten-based amorphous alloy comprises any one or a combination of two or more of powder, film, wire, strip, and block. The amorphous alloy in this form can be prepared by preparing a master alloy having the aforementioned elemental composition ratio and rapidly solidifying the molten liquid of the master alloy by quenching. For example, a strip (wire) method can be used to spray the molten liquid of the master alloy onto a rotating copper roller to prepare a thin strip; a thin film can also be prepared by magnetron sputtering; a powder can be prepared by ball milling or atomization; and a block can be formed by die casting or suction casting.

[0036] In some embodiments of the present invention, the ultra-wear-resistant and high-temperature tungsten-based amorphous alloy provided has a diameter of more than 1.5 mm, preferably more than 2 mm, preferably 2 mm.

[0037] In some embodiments of the present invention, a super wear-resistant and high-temperature tungsten-based amorphous alloy is provided, wherein the glass transition temperature of the super wear-resistant and high-temperature tungsten-based amorphous alloy is 780-840°C and the crystallization temperature is 820-900°C.

[0038] In some embodiments of the present invention, a super wear-resistant and high-temperature tungsten-based amorphous alloy is provided, wherein the room temperature compressive strength of the super wear-resistant and high-temperature tungsten-based amorphous alloy is 5 to 6 GPa.

[0039] In some embodiments of the present invention, a super wear-resistant and high-temperature tungsten-based amorphous alloy is provided, wherein the Young's modulus of the super wear-resistant and high-temperature tungsten-based amorphous alloy is 240 to 300 GPa.

[0040] In some embodiments of the present invention, a super wear-resistant and high-temperature tungsten-based amorphous alloy is provided, wherein the microhardness of the super wear-resistant and high-temperature tungsten-based amorphous alloy is 1500-1700 HV.

[0041] In some embodiments of the present invention, a super wear-resistant high temperature tungsten-based amorphous alloy is provided, wherein the room temperature friction coefficient of the super wear-resistant high temperature tungsten-based amorphous alloy is 0.28-0.37, and the room temperature wear rate is 1.6×10 -7 ~1.2×10 -6 mm 3 / Nm.

[0042] In some embodiments of the present invention, a method for preparing an ultra-wear-resistant, high-temperature tungsten-based amorphous alloy is provided, comprising the following preparation steps:

[0043] S1. Weigh the raw materials according to the alloy composition: The chemical formula of the super wear-resistant tungsten-based amorphous alloy is: W a Fe b B c C d , wherein a, b, c, and d represent the atomic percentage content of the corresponding chemical elements, a=23-48, b=32-57, c=14-18, d=2-6, and a+b+c+d=100;

[0044] S2 raw material smelting to prepare a master alloy ingot: The raw material weighed in step S1 is uniformly smelted in a vacuum or protective atmosphere to prepare a master alloy ingot;

[0045] S3. Suction casting of the master alloy ingot into a water-cooled copper mold: The master alloy ingot prepared in step S2 is heated and smelted, and then suction cast into a water-cooled copper mold for cooling to prepare a high-temperature tungsten-based amorphous alloy.

[0046] The present invention is described in detail below with reference to specific embodiments.

[0047] Example 1:

[0048] This embodiment provides an ultra-wear-resistant, high-temperature tungsten-based amorphous alloy and a preparation method thereof, specifically comprising the following steps:

[0049] S1. Weigh the raw materials according to the alloy composition: the chemical formula of the alloy composition is W 23 Fe 57 B 16 C4, represents the components and the atomic percentage of each component as follows: W: 23%; Fe: 57%; B: 16%; C: 4%, and the raw materials are tungsten, iron, boron and carbon with a purity of not less than 99.9wt.%;

[0050] S2. Raw material smelting to prepare master alloy ingot: The raw materials weighed in step S1 are placed in the first copper crucible of the arc melting furnace, and sponge titanium is placed in the second copper crucible. The arc melting furnace is evacuated to 6×10 -3Pa, turn off the molecular pump, fill with argon to positive pressure, melt the titanium sponge in the second copper crucible to remove the residual impurity gas in the furnace, and then repeatedly melt the raw materials in the first copper crucible to obtain a master alloy ingot with uniform composition;

[0051] S3. Suction casting of master alloy ingot into water-cooled copper mold: The master alloy ingot prepared in step S2 is heated and smelted, and then suction cast into water-cooled copper molds with inner cavity diameters of 1.5 mm and 2 mm. After cooling, it is taken out to prepare 1.5 mm sample W1-1 and 2 mm sample W1-2.

[0052] The amorphous structure of the sample was characterized by XRD diffractometer, such as Figure 1 As shown, only one diffuse peak was detected in sample W1-1 of Example 1, and no sharp diffraction peaks from the crystalline phase were detected, indicating that the 1.5 mm W1-1 sample prepared in Example 1 had a completely amorphous structure. Observation of sample W1-2 under a metallographic microscope revealed the presence of a crystalline phase, indicating that the 2 mm W1-2 sample was an amorphous composite material.

[0053] Example 2:

[0054] Example 2 provides an ultra-wear-resistant, high-temperature tungsten-based amorphous alloy and a preparation method thereof, which specifically includes the following steps:

[0055] S1. Weigh the raw materials according to the alloy composition: the chemical formula of the alloy composition is W 36 Fe 44 B 16 C4, represents the components and the atomic percentage of each component as follows: W: 36%; Fe: 44%; B: 16%; C: 4%, and the raw materials are tungsten, iron, boron and carbon with a purity of not less than 99.9wt.%;

[0056] S2. Raw material smelting to prepare master alloy ingot: The raw materials weighed in step S1 are placed in the first copper crucible of the arc melting furnace, and sponge titanium is placed in the second copper crucible. The arc melting furnace is evacuated to 6×10 -3 Pa, turn off the molecular pump, fill with argon to positive pressure, melt the titanium sponge in the second copper crucible to remove the residual impurity gas in the furnace, and then repeatedly melt the raw materials in the first copper crucible to obtain a master alloy ingot with uniform composition;

[0057] S3. Suction casting of the master alloy ingot into a water-cooled copper mold: The master alloy ingot prepared in step S2 is heated and smelted, and then suction-cast into a water-cooled copper mold with an inner cavity diameter of 2 mm. After cooling, it is taken out to prepare sample W2.

[0058] The amorphous structure of the sample was characterized by XRD diffractometer, such as Figure 1As shown, only one diffuse peak was detected for the sample W2 of Example 2, and no sharp diffraction peak from the crystalline phase was detected, indicating that the 2 mm W2 sample prepared in Example 2 was a completely amorphous structure.

[0059] Example 3:

[0060] Example 3 provides an ultra-wear-resistant, high-temperature tungsten-based amorphous alloy and a preparation method thereof, which specifically includes the following steps:

[0061] S1. Weigh the raw materials according to the alloy composition: the chemical formula of the alloy composition is W 40 Fe 40 B 16 C4, represents the components and the atomic percentage of each component as follows: W: 40%; Fe: 40%; B: 16%; C: 4%, and the raw materials are tungsten, iron, boron and carbon with a purity of not less than 99.9wt.%;

[0062] S2. Raw material smelting to prepare master alloy ingot: The raw materials weighed in step S1 are placed in the first copper crucible of the arc melting furnace, and sponge titanium is placed in the second copper crucible. The arc melting furnace is evacuated to 6×10 -3 Pa, turn off the molecular pump, fill with argon to positive pressure, melt the titanium sponge in the second copper crucible to remove the residual impurity gas in the furnace, and then repeatedly melt the raw materials in the first copper crucible to obtain a master alloy ingot with uniform composition;

[0063] S3. Suction casting of the master alloy ingot into a water-cooled copper mold: The master alloy ingot prepared in step S2 was heated and smelted, and then suction-cast into a water-cooled copper mold with an inner cavity diameter of 2 mm. After cooling, it was taken out to prepare sample W3.

[0064] The amorphous structure of the sample was characterized by XRD diffractometer, such as Figure 1 As shown, only one diffuse peak was detected for the sample W3 of Example 3, and no sharp diffraction peak from the crystalline phase was detected, indicating that the 2 mm W3 sample prepared in Example 3 was a completely amorphous structure.

[0065] Neutron scattering technology was used to characterize the amorphous structure of the sample. The neutron scattering spectrum of the sample W3 prepared in Example 3 is as follows: Figure 2 As shown, from Figure 2 It can be seen that the spectrum of sample W3 is a smooth curve, and no crystalline phase is detected at the nanoscale, indicating that the 2 mm sample prepared in Example 3 is a completely amorphous structure.

[0066] The thermal stability of the samples was investigated using a differential thermal analyzer with a heating rate of 20°C / min. Figure 3As shown, the glass transition temperature of sample W3 of Example 3 was measured to be 788° C., and the crystallization temperature was measured to be 820° C., indicating that sample W3 has good high-temperature stability.

[0067] The room temperature compressive strength of the sample was tested by a universal mechanical testing machine. Figure 4 As shown, the room temperature compressive strength of sample W3 of Example 3 was measured to be 5.1 GPa.

[0068] The Young's modulus of the samples was studied by nanoindentation. Figure 5 As shown, it is calculated that the Young's modulus of the sample W3 of Example 3 is 240 GPa.

[0069] The microhardness of the sample was studied by microhardness tester, such as Figure 6 As shown, the microhardness of sample W3 of Example 3 is 1595±17 HV.

[0070] The wear resistance of the samples was tested by friction and wear tester. Figure 7 As shown, the friction coefficient of sample W3 of Example 3 is 0.28.

[0071] The wear rate of the samples was calculated by profilometer, as shown in Figure 8 As shown in the figure, the wear rate of sample W3 in Example 3 is 1.6×10 -7 mm 3 / Nm.

[0072] Example 4:

[0073] Example 4 provides an ultra-wear-resistant, high-temperature tungsten-based amorphous alloy and a preparation method thereof, which specifically includes the following steps:

[0074] S1. Weigh the raw materials according to the alloy composition: the chemical formula of the alloy composition is W 44 Fe 36 B 16 C4, represents the components and the atomic percentage of each component as follows: W: 44%; Fe: 36%; B: 16%; C: 4%, and the raw materials are tungsten, iron, boron and carbon with a purity of not less than 99.9wt.%;

[0075] S2. Raw material smelting to prepare master alloy ingot: The raw materials weighed in step S1 are placed in the first copper crucible of the arc melting furnace, and sponge titanium is placed in the second copper crucible. The arc melting furnace is evacuated to 6×10 -3 Pa, turn off the molecular pump, fill with argon to positive pressure, melt the titanium sponge in the second copper crucible to remove the residual impurity gas in the furnace, and then repeatedly melt the raw materials in the first copper crucible to obtain a master alloy ingot with uniform composition;

[0076] S3. Suction casting of master alloy ingot into water-cooled copper mold: The master alloy ingot prepared in step S2 is heated and smelted, and then suction cast into water-cooled copper molds with inner cavity diameters of 1.5 mm and 2 mm. After cooling, it is taken out to prepare 1.5 mm sample W4-1 and 2 mm sample W4-2.

[0077] The same test method as in Example 1 was used to characterize the amorphous structure of the sample. Figure 1 As shown, the diffraction peaks of sample W4-1 in Example 4 only detected a diffuse peak, and no sharp diffraction peaks from the crystalline phase were detected, indicating that sample W4-1 has a completely amorphous structure. Metallographic microscopy observation of sample W4-2 showed the presence of a partial crystalline phase, indicating that the 2 mm sample W4-2 is an amorphous composite material.

[0078] Example 5:

[0079] Example 5 provides an ultra-wear-resistant, high-temperature tungsten-based amorphous alloy and a preparation method thereof, which specifically includes the following steps:

[0080] S1. Weigh the raw materials according to the alloy composition: the chemical formula of the alloy composition is W 48 Fe 32 B 16 C4, represents the components and the atomic percentage of each component as follows: W: 48%; Fe: 32%; B: 16%; C: 4%, and the raw materials are tungsten, iron, boron and carbon with a purity of not less than 99.9wt.%;

[0081] S2. Raw material smelting to prepare master alloy ingot: The raw materials weighed in step S1 are placed in the first copper crucible of the arc melting furnace, and sponge titanium is placed in the second copper crucible. The arc melting furnace is evacuated to 6×10 -3 Pa, turn off the molecular pump, fill with argon to positive pressure, melt the titanium sponge in the second copper crucible to remove the residual impurity gas in the furnace, and then repeatedly melt the raw materials in the first copper crucible to obtain a master alloy ingot with uniform composition;

[0082] S3. Suction casting of master alloy ingot into water-cooled copper mold: The master alloy ingot prepared in step S2 is heated and smelted, and then suction cast into water-cooled copper molds with inner cavity diameters of 1.5 mm and 2 mm. After cooling, it is taken out to prepare 1.5 mm sample W5-1 and 2 mm sample W5-2.

[0083] The amorphous structure of the sample was characterized by an X-ray diffractometer. The XRD pattern of the sample W5-1 prepared in Example 5 is as follows: Figure 1 As shown, from Figure 1As can be seen from the figure, only a diffuse peak was detected for the diffraction peak of sample W5-1, and no sharp diffraction peaks from the crystalline phase were detected, indicating that the 1.5 mm sample W5-1 prepared in Example 5 had a completely amorphous structure. Metallographic microscopy observation of sample W5-2 showed the presence of a partial crystalline phase, indicating that the 2 mm sample W5-2 was an amorphous composite material.

[0084] Neutron scattering technology was used to characterize the amorphous structure of the sample. The neutron scattering spectrum of the sample W5-1 prepared in Example 5 is as follows: Figure 2 As shown, from Figure 2 It can be seen that the spectrum of sample W5-1 is a smooth curve, and no crystalline phase is detected at the nanoscale, indicating that the 1.5 mm sample W5-1 prepared in Example 5 is a completely amorphous structure.

[0085] The thermal stability of the samples was investigated using a differential thermal analyzer with a heating rate of 20°C / min. Figure 3 As shown, the glass transition temperature of sample W5-1 of Example 5 was measured to be 840° C., and the crystallization temperature was measured to be 894° C., indicating that sample W5-1 has good high-temperature stability.

[0086] The room temperature compressive strength of the sample was tested by a universal mechanical testing machine. Figure 4 As shown, the room temperature compressive strength of sample W5-1 of Example 5 is 5.6 GPa.

[0087] The Young's modulus of the samples was studied by nanoindentation. Figure 5 As shown, after calculation, the Young's modulus of the sample W5-1 of Example 5 is 296 GPa.

[0088] The microhardness of the sample was studied by microhardness tester, such as Figure 6 As shown, the microhardness of sample W5-1 of Example 5 is 1650±20 HV.

[0089] The wear resistance of the samples was tested by friction and wear tester. Figure 7 As shown, the friction coefficient of sample W5-1 of Example 5 is 0.37.

[0090] The wear rate of the samples was calculated by profilometer, as shown in Figure 8 As shown in the figure, the wear rate of sample W5-1 in Example 5 is 1.2×10 -6 mm 3 / Nm.

[0091] The amorphous samples of Examples 1, 2, and 4 were tested using the same testing method as that of Examples 3 and 5. It was found that the amorphous samples of Examples 1, 2, and 4 also had excellent comprehensive properties.

[0092] The above embodiments are merely preferred embodiments for the purpose of fully illustrating 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 within the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

Claims

1. A super wear-resistant high temperature tungsten-based amorphous alloy, characterized in that: The chemical formula of the super wear-resistant high temperature tungsten-based amorphous alloy is: a Fe b B c C d , wherein a, b, c, and d represent the atomic percentage content of the corresponding chemical elements, a=23-48, b=32-57, c=14-18, d=2-6, and a+b+c+d=100, the super wear-resistant high-temperature tungsten-based amorphous alloy is composed of a single amorphous phase; the block diameter of the super wear-resistant high-temperature tungsten-based amorphous alloy is greater than 1.5 mm; the glass transition temperature of the super wear-resistant high-temperature tungsten-based amorphous alloy is between 780 and 840°C, and the crystallization temperature is between 820 and 900°C; the room temperature friction coefficient of the super wear-resistant high-temperature tungsten-based amorphous alloy is between 0.28 and 0.37, and the room temperature wear rate is 1.6×10 -7 ~1.2×10 -6 mm 3 / Nm.

2. The ultra-wear-resistant and high-temperature tungsten-based amorphous alloy according to claim 1, characterized in that: a=34~42, b=38~46, c=14~18, d=2~6, and a+b+c+d=100.

3. The ultra-wear-resistant and high-temperature tungsten-based amorphous alloy according to claim 1 or 2, characterized in that: The block diameter of the ultra-wear-resistant and high-temperature tungsten-based amorphous alloy is greater than 2 mm.

4. The ultra-wear-resistant and high-temperature tungsten-based amorphous alloy according to claim 1 or 2, characterized in that: The ultra-wear-resistant high-temperature tungsten-based amorphous alloy has a room temperature compressive strength of 5-6 GPa, a Young's modulus of 240-300 GPa, and a microhardness of 1500-1700 HV.

5. A method for preparing the ultra-wear-resistant and high-temperature tungsten-based amorphous alloy according to any one of claims 1 to 4, characterized in that: The block of the ultra-wear-resistant and high-temperature tungsten-based amorphous alloy is formed by a suction casting method, including the following preparation steps: S1. Weigh the raw materials according to the alloy composition: The chemical formula of the ultra-wear-resistant high-temperature tungsten-based amorphous alloy is: W a Fe b B c C d , where a, b, c, and d represent the atomic percentage content of the corresponding chemical elements, a=23~48, b=32~57, c=14~18, d=2~6, and a+b+c+d=100; S2 raw material smelting to prepare a master alloy ingot: The raw material weighed in step S1 is uniformly melted in a vacuum or protective atmosphere to prepare a master alloy ingot; S3. Suction casting of the master alloy ingot into a water-cooled copper mold: The master alloy ingot prepared in step S2 is heated and smelted, and then suction cast into a water-cooled copper mold for cooling to prepare a high-temperature tungsten-based amorphous alloy.

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