Os-based high-temperature amorphous alloy material and preparation method thereof

Abstract

This invention provides an Os-based high-temperature amorphous alloy material and its preparation method. The chemical formula of the Os-based high-temperature amorphous alloy material is Os... a B b M c The alloy is primarily composed of Os, with B as the secondary element, and M including at least one of Zr, Hf, V, Ta, and W. a, b, and c represent the atomic percentages of the corresponding elements: a = 39–50, b = 34–44, c = 12–24, and the sum of the atomic percentages of all elements (a + b + c) = 100. The Os-based high-temperature amorphous alloy material provided by this invention exhibits high glass transition temperature and crystallization temperature, while also possessing excellent room-temperature and high-temperature mechanical properties. Experimental data shows that its glass transition temperature is 1040 K–1283 K; and its Vickers microhardness value is above 16.74 GPa. Furthermore, in terms of preparation methods, this invention also provides a method for rapid verification of the alloy composition of the amorphous alloy by combining laser melting and XRD phase analysis.

Description

Technical Field

[0001] This invention belongs to the field of amorphous alloy material development and preparation technology, specifically relating to an Os-based high-temperature amorphous alloy material and its preparation method. Background Technology

[0002] Amorphous alloys, due to their unique thermoplastic forming properties, isotropy, uniform microstructure, low coefficient of thermal expansion, and atomically smooth surface finish, are ideal materials for precision glass forming molds and have significant application prospects in the glass molding field. The operating temperature of glass molding molds often exceeds 973K (700℃). However, limited by glass transition temperature, thermal stability, and glass-forming ability, the service temperature of traditional amorphous alloys is generally below 600K, making them unsuitable for manufacturing glass molding molds.

[0003] Amorphous alloys with a glass transition temperature exceeding 973K are called high-temperature amorphous alloys, which possess unparalleled mechanical property advantages over crystalline materials. For example, they exhibit high strength and hardness at room temperature and maintain extremely high strength even before their glass transition temperature, making them promising candidates for meeting the mechanical performance requirements of molds in precision manufacturing fields such as optical component molding. Currently, ternary systems such as IrNiTa and MoCoB have been developed (glass forming capability ≥1mm, glass transition temperature ≥973K). However, high-temperature bulk amorphous alloy systems with even superior performance remain to be developed.

[0004] Compositional design guided by high-modulus elements is an important approach for the development of high-strength amorphous alloys. As the pure metallic element with the highest modulus, Os has not yet been developed into an amorphous alloy system based on it. Furthermore, ternary alloys have a wide compositional range. How to quickly screen alloy components with glass-forming capabilities to develop new Os-based high-temperature amorphous alloy materials, thereby addressing the urgent need for materials in optical glass molding dies and providing key materials and technologies for my country's advanced manufacturing industry, is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0005] The purpose of this invention is to provide an Os-based high-temperature amorphous alloy material with the chemical formula Os. a B b M c It is based on Os (osmium) as the main element, with boron (B) as the secondary element, and M including at least one of Zr (zirconium), Hf (hafnium), V (vanadium), Ta (tantalum), and W (tungsten). a, b, and c are the atomic percentages (at%) of the corresponding elements, where a = 39–50, b = 34–44, and c = 12–24, and the sum of the atomic percentages of all elements a + b + c = 100.

[0006] In a preferred embodiment, the glass transition temperature of the Os-based high-temperature amorphous alloy material is 1040K-1283K.

[0007] In a preferred embodiment, the Vickers microhardness value of the Os-based high-temperature amorphous alloy material is above 16.74 GPa.

[0008] The Os-based high-temperature amorphous alloy material provided by this invention can simultaneously achieve a high glass transition temperature and high mechanical properties. Its glass transition temperature can reach 1283K, which is far superior to existing amorphous alloy materials. At the same time, its mechanical properties, such as elastic modulus, Vickers microhardness, room temperature compressive strength, and compressive strength at 1000K, are all significantly higher than those of existing amorphous alloy materials.

[0009] In a preferred embodiment, in the Os-based high-temperature amorphous alloy material, when the M element is the Hf element, the atomic percentages of each element are a = 42-50, b = 34-42, and c = 12-20, respectively, and a + b + c = 100.

[0010] In a preferred embodiment, the Os a B b Hf c The glass transition temperature of the high-temperature amorphous alloy material is 1231K, and the Vickers microhardness is 18.06GPa.

[0011] In a preferred embodiment, the Os 46 B 38 Hf 16 The high-temperature amorphous alloy material has a Young's modulus of 299 GPa, a compressive fracture strength of 6.8 GPa at room temperature, and a compressive yield strength of 3.9 GPa at 1000 K.

[0012] In a preferred embodiment, the Os-based high-temperature amorphous alloy composition includes Os. 45 B 35 Zr 20 Os 45 B 35 V 20 Os 50 B 35 Ta 15 and Os 45 B 35 W 20 .

[0013] Another object of the present invention is to provide a method for preparing Os-based high-temperature amorphous alloy materials, specifically including:

[0014] Step 1: According to the chemical formula Os-based high-temperature amorphous alloy...a B b M c Calculate the mass ratio of each element and weigh and mix the ingredients; element M includes at least one of Zr, Hf, V, Ta and W; a, b and c are the atomic percentages of the corresponding elements, a = 39-50, b = 34-44, c = 12-24, and the sum of the atomic percentages of each element a + b + c = 100;

[0015] Step 2: Use induction melting to melt each element into a master alloy ingot;

[0016] Step 3: The master alloy ingot obtained in Step 2 is heated and melted in a protective atmosphere, and Os-based high-temperature amorphous alloy strips are prepared by melt spin quenching; or the master alloy ingot obtained in Step 2 is heated and melted in a protective atmosphere, and Os-based high-temperature amorphous alloy blocks are prepared by copper mold casting.

[0017] In a preferred embodiment, step 2 specifically includes the following steps:

[0018] S1 melts Os using induction melting. 50 B 50 Alloying: Place the boron nitride crucible containing Os metal raw material and B elemental raw material into a vacuum induction melting furnace, and evacuate to a vacuum degree ≤3.0×10. -2 Pa, fill with 0.05MPa high-purity Ar gas; under Ar gas protection and a melting temperature of 1000-2000℃, melt for 3-15 minutes, repeat the melting process 2-5 times, and remove after cooling;

[0019] S2 will obtain Os from induction melting 50 B 50 The alloy ingot is placed in a vacuum electric arc furnace, and Os and M elements are added according to the designed alloy composition ratio. The furnace is then evacuated to a vacuum degree ≤ 8 × 10⁻⁶. -3 Pa, filled with 0.05MPa high-purity Ar gas; under Ar gas protection, melted by electric arc at 2000℃~3000℃ for 3~15min, repeated 5 times, cooled and taken out to prepare the master alloy.

[0020] Due to the anisotropic thermal expansion of elemental B, direct vacuum arc melting would cause B to splatter, resulting in an alloy composition that does not match the nominal composition. Therefore, in this invention, element B is first melted together with other metallic elements (Os).

[0021] In a preferred embodiment, the melt spin quenching method in step 3 specifically includes:

[0022] The master alloy obtained in step 2 is placed in a rapid solidification induction furnace and evacuated to a vacuum level ≤ 1 × 10⁻⁻¹. 2The process involves filling the tube with 0.05 MPa of high-purity Ar gas and heating it to a temperature of 1800–2000 °C. The rotation speed of the rapid solidification copper wheel is adjusted to 1000–3000 r / min, the injection pressure is 0.01–0.02 MPa, and the copper is induction heated to melt it for 10–60 seconds. The melt is then sprayed onto the surface of the high-speed rotating copper wheel to obtain an Os-based amorphous alloy thin strip.

[0023] In a preferred embodiment, after step 2 and before step 3, a rapid screening and verification of alloy components with glass-forming capabilities is further included, specifically comprising the following steps:

[0024] The master alloy ingot obtained in step 2 was cut into thin slices with a thickness of 3 mm. The surface of the thin slices was treated by laser melting and quenching technology to obtain an Os-based high-temperature amorphous alloy remelting layer. The phase analysis of the remelting layer showed that the remelting layer had broadened diffuse diffraction peaks, that is, it had a certain glass-forming ability.

[0025] Preferably, the laser melting and quenching technology for thin-film surface treatment specifically includes:

[0026] The homogenized master alloy ingot, obtained through induction melting and arc melting, is cut to obtain a 3mm thick, parallel plane. The wire cutting marks are then ground and polished to ensure the master alloy sample surface is free of oxide and has a metallic luster. The polished sample is placed on a laser processing stage, which is protected by high-purity Ar gas. The laser type is a pulsed laser with a power of 220W, a voltage of 60V, a frequency of 15Hz, a pulse interval of 1ms, a path spacing of 0.2mm, and a laser movement speed of 180mm / min.

[0027] In this invention, the master alloy ingot is cut into thin slices, and surface treatment is performed using laser melting and quenching technology to obtain an Os-based high-temperature amorphous alloy remelted layer. This allows for rapid verification of the master alloy composition that forms the amorphous structure. The results confirm that the remelted layer has broadened diffuse diffraction peaks, indicating that it possesses a certain glass-forming ability. This step, through master alloy melting, laser melting and quenching surface processing, and XRD phase testing, can quickly screen and verify alloy components with glass-forming ability. It has advantages such as saving raw materials and rapid component development, and is far superior to traditional amorphous alloy development methods in terms of development efficiency and resource utilization.

[0028] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0029] This invention uses the high-modulus element Os as the main alloying element, with the small-atomic element B as the secondary element, and also includes at least one of Zr, Hf, V, Ta, and W elements for composition design. A master alloy ingot with the corresponding composition is then melted using induction melting or arc melting. Finally, the master alloy ingot is subjected to amorphous alloy preparation, and Os-based high-temperature amorphous alloy strips or bulk materials can be obtained using melt spin quenching or copper mold casting. After obtaining the master alloy ingot, the amorphous structure of the material can be rapidly verified by laser quenching surface processing and XRD phase testing, further improving development efficiency.

[0030] The Os-based high-temperature amorphous alloy material prepared by this invention has the characteristics of multiple components and a wide range of compositional variations, allowing for adjustment of the composition of each component within a broad range, which is beneficial for industrial applications. Furthermore, the Os-based high-temperature amorphous alloy material prepared by this invention exhibits the highest elastic modulus, the highest Vickers microhardness, the highest glass transition temperature, the highest room-temperature compressive strength, and the highest compressive strength at 1000K among existing high-temperature bulk amorphous alloys. Due to its excellent room-temperature and high-temperature mechanical properties, it can be widely used in the field of precision glass forming mold materials. Attached Figure Description

[0031] These and / or other aspects and advantages of the present invention will become clearer and more readily understood from the following detailed description of embodiments of the invention taken in conjunction with the accompanying drawings, wherein:

[0032] Figure 1 Os in Embodiment 1 of the present invention 46 B 38 Hf 16 XRD patterns of alloy thin sheets after laser remelting;

[0033] Figure 2 Os in Embodiment 1 of the present invention 46 B 38 Hf 16 XRD pattern of a 1mm amorphous alloy sample;

[0034] Figure 3 Os in Embodiment 1 of the present invention 46 B 38 Hf 16 DSC curve of a 1mm amorphous alloy sample;

[0035] Figure 4 Os in Embodiment 1 of the present invention 46 B 38 Hf 16 Compression curves of 1 mm amorphous alloy samples at room temperature and 1000 K;

[0036] Figure 5 Os in Embodiment 2 of the present invention45 B 35 Zr 20 Os 45 B 35 V 20 Os 50 B 35 Ta 15 and Os 45 B 35 W 20 XRD patterns of alloy thin sheets after laser remelting;

[0037] Figure 6 Os in Embodiment 2 of the present invention 45 B 35 Zr 20 Os 45 B 35 V 20 Os 50 B 35 Ta 15 and Os 45 B 35 W 20 XRD pattern of amorphous alloy strip sample. Detailed Implementation

[0038] To enable those skilled in the art to better understand the present invention, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. However, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments.

[0039] The technical solution of this application will be described in detail below through specific embodiments:

[0040] Unless otherwise specified, the technical means used in this invention are conventional means well known to those skilled in the art. All raw materials, reagents, instruments, and equipment used in this invention can be purchased commercially or prepared using existing methods. Unless otherwise specified, all reagents used in this invention are of analytical grade. The purity of the elemental substances used in this invention is ≥99.95%.

[0041] Example 1:

[0042] Step 1: Os a B b M c The alloy composition design uses M as Hf, with the specific atomic ratio of each element being Os. 46 B 38 Hf 16 .

[0043] Step 2: According to the Os design above 46 B 38 Hf 16The alloy was calculated based on the atomic ratios and relative atomic masses of each element. The required mass of each element for producing 3g of the alloy was determined. Os was first melted using induction melting. 50 B 50 The alloy, with a vacuum degree of 8×10 before melting. -3 Pa, Ar is introduced as a protective atmosphere during the melting process, and the alloy is melted at 1800℃ for 3 minutes, and the melting is repeated 5 times to ensure uniform alloy composition.

[0044] Then melt the Os 50 B 50 The alloy and elemental Os and Hf are smelted together in a vacuum arc furnace to form a master alloy ingot with a pre-designed composition. The vacuum level is evacuated to 8 × 10⁻⁶ before smelting. -3 Below Pa, Ar is introduced as a protective atmosphere during the melting process, and the alloy is melted at 2500℃ for 3 minutes. The melting is repeated 5 times to ensure uniform alloy composition.

[0045] The homogeneous master alloy obtained in step 2 was machined into alloy sheets with a thickness of 3 mm. The alloy sheets were then polished and laser remelted using a pulsed laser at a power of 220 W and a scanning speed of 180 mm / min in an Ar atmosphere to obtain Os. 46 Hf 16 B 38 High-temperature amorphous alloy remelted layer. Phase analysis of the remelted layer was performed using XRD at a scan rate of 6° / min and a scan range of 20°–80°. The XRD pattern of the laser-remelted layer is shown below. Figure 1 As shown, it can be seen that Os 46 B 38 Hf 16 The alloy exhibits broadened diffuse diffraction peaks in the laser remelting layer, indicating that the alloy possesses a certain glass-forming ability.

[0046] Step 3: The alloy ingot obtained in Step 2 is heated and melted in a protective atmosphere, then sprayed into a copper mold to obtain a 1mm thick Os-based high-temperature amorphous alloy block. Specific conditions for the copper mold casting method include: evacuating to a vacuum level of 1×10⁻⁶. -2 The mixture is filled with 0.05 MPa of high-purity Ar gas and heated to 2000℃. The injection pressure is 0.02 MPa, and the mixture is induction heated for 30 seconds before being injected into a 1 mm thick copper mold to obtain the final product.

[0047] The performance of the Os-based high-temperature amorphous alloy bulk prepared in Example 1 was tested, and the results are as follows:

[0048] The 1 mm Os obtained in step 3 was analyzed by XRD. 46 B 38 Hf 16Phase analysis was performed on the amorphous alloy bulk material using XRD at a scanning speed of 6° / min and a scanning range of 20°–80°. The results are as follows: Figure 2 As can be seen from the figure, the XRD pattern shows obvious broadened diffuse scattering peaks, and no other crystal diffraction peaks appear, indicating that the prepared bulk materials are all completely amorphous structures.

[0049] The prepared 1 mm Os was tested using differential scanning calorimetry (DSC). 46 B 38 Hf 16 Thermal properties of amorphous alloys were measured at a heating rate of 20 K / min, with a sample mass of 20 mg. Figure 3 As shown. Its glass transition temperature T g The crystallization initiation temperature is 1231 K, T. x The K value is 1269 K. Its density ρ, measured using Archimedes' displacement method, is 16.48 g / cm³. 3 Microhardness Hv 0.2 The maximum pressure was 18.06 GPa. Its elastic properties were tested using ultrasonic testing; the elastic modulus E was 299 GPa, the shear modulus G was 112 GPa, and the bulk modulus B was 303 GPa. Specific data are shown in Table 1. Room temperature and high temperature compression performance curves are shown below. Figure 4 As shown, the room temperature fracture strength is 6.8 GPa, and the compressive yield strength at 1000 K is 3.9 GPa.

[0050] Table 1Os 46 B 38 Hf 16 Performance table of 1mm amorphous alloy samples

[0051]

[0052] Example 2

[0053] Step 1: Os a B b M c The alloy composition is designed with M elements representing Zr, V, Ta, and W, and the specific atomic ratio of each element is Os. 45 B 35 Zr 20 Os 45 B 35 V 20 Os 50 B 35 Ta 15 and Os 45 B 35 W 20 .

[0054] Step 2: According to the Os design above 45 B35 Zr 20 Os 45 B 35 V 20 Os 50 B 35 Ta 15 and Os 45 B 35 W 20 The alloy was calculated based on the atomic ratios and relative atomic masses of each element. The required mass of each element for producing 3g of the alloy was determined. Os was first melted using induction melting. 50 B 50 The alloy, with a vacuum degree of 8×10 before melting. -3 Pa, Ar is used as a protective atmosphere during the melting process, and the alloy is melted at 1800℃ for 3 minutes, repeated 5 times to ensure uniform alloy composition. Then the melted Os... 50 B 50 The alloy and elemental Os, V, Ta, and W are smelted together in a vacuum arc furnace to form a master alloy ingot with a pre-designed composition. The vacuum level is evacuated to 8 × 10⁻⁶ before smelting. - 3 Below Pa, Ar is introduced as a protective atmosphere during the melting process, and the alloy is melted at 2500℃ for 3 minutes. The melting is repeated 5 times to ensure uniform alloy composition.

[0055] The homogeneous master alloy obtained in step 2 was machined into alloy sheets with a thickness of 3 mm. The alloy sheets were then polished and laser remelted using a pulsed laser at a power of 220 W and a scanning speed of 180 mm / min in an Ar atmosphere to obtain Os. 45 B 35 Zr 20 Os 45 B 35 V 20 Os 50 B 35 Ta 15 and Os 45 B 35 W 20 High-temperature amorphous alloy remelted layer. Phase analysis of the remelted layer was performed using XRD at a scan rate of 6° / min and a scan range of 20°–80°. The XRD pattern of the laser-remelted layer is shown below. Figure 5 As shown in the figure, the remelted layer has broadened diffuse ray peaks, indicating that the above alloy has a certain glass-forming ability.

[0056] Step 3: The alloy ingot obtained in Step 2 is heated and melted in a protective atmosphere, and Os with a thickness of 30 μm is obtained by melt spin quenching. 45 B35 Zr 20 Os 45 B 35 V 20 Os 50 B 35 Ta 15 Thin strip sample. The specific reaction conditions for the melt spin quenching method used included: evacuation to a vacuum level of 1×10⁻⁶. -2 Pa, filled with 0.05MPa high-purity Ar gas, heated to 2000℃. Adjust the rotation speed of the rapid solidification copper wheel to 3000r / min, the injection pressure to 0.02MPa, and induction heat to melt it for 30s. Then spray it onto the surface of the high-speed rotating copper wheel to obtain the product.

[0057] The Os prepared in Example 2 45 B 35 Zr 20 Os 45 B 35 V 20 Os 50 B 35 Ta 15 The performance of high-temperature amorphous alloy strips was tested, and the results are as follows:

[0058] The Os obtained in step 3 was analyzed using XRD. 45 B 35 Zr 20 Os 45 B 35 V 20 Os 50 B 35 Ta 15 and Os 45 B 35 W 20 Phase analysis was performed on amorphous alloy strips using XRD at a scanning speed of 6° / min and a scanning range of 20°–80°. The results are as follows: Figure 6 As can be seen from the figure, the XRD pattern shows obvious broadened diffuse scattering peaks, and no other crystal diffraction peaks appear, indicating that the prepared bulk materials are all completely amorphous structures.

[0059] The prepared Os was tested using differential scanning calorimetry (DSC). 45 B 35 Zr 20 Os 45 B 35 V 20 Os 50 B 35 Ta 15 and Os 45 B 35 W 20The thermal properties of amorphous alloy strip samples were tested using a sample mass of 20 mg and a heating rate of 20 K / min. The density ρ was measured using the Archimedes' displacement method. The microhardness Hv was measured using a Vickers microhardness tester. 0.2 The performance data above is shown in Table 2.

[0060] Table 2Os 45 B 35 Zr 20 Os 45 B 35 V 20 Os 50 B 35 Ta 15 and Os 45 B 35 W 20 Performance table of amorphous alloy strip samples

[0061]

[0062] As can be seen from the table, Os 45 B 35 Zr 20 Glass transition temperature T g Its K value is 1283K, and its microhardness Hv is also high. 0.2 Up to 18.44 GPa.

[0063] The foregoing description of specific exemplary embodiments of the invention is for illustrative and explanatory purposes. These descriptions are not intended to limit the invention to the precise forms disclosed, and it will be apparent that many changes and variations can be made in accordance with the foregoing teachings. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application, thereby enabling those skilled in the art to implement and utilize various different exemplary embodiments of the invention, as well as various different choices and variations. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. An Os-based high-temperature amorphous alloy material, characterized in that, The chemical formula of the Os-based high-temperature amorphous alloy material is Os a B b M c ; where element M includes at least one of Zr, Hf, V, Ta and W; a, b and c are the atomic percentages of the corresponding elements, a=39~50, b=34~44, c=12~24, and the sum of the atomic percentages of each element a+b+c=100; The glass transition temperature of the Os-based high-temperature amorphous alloy material is 1040K-1283K; The Vickers microhardness value of the Os-based high-temperature amorphous alloy material is above 16.74 GPa; In the Os-based high-temperature amorphous alloy material, when the M element is Hf, the atomic percentages of each element are a=42~50, b=34~42, and c=12~20, and when a+b+c=100, the Os... a B b Hf c The glass transition temperature of the high-temperature amorphous alloy material is 1231K, the Vickers microhardness is 18.06GPa, the Young's modulus is 299GPa, the compressive fracture strength at room temperature is 6.8GPa, and the compressive yield strength at 1000K is 3.9GPa.

2. The Os-based high-temperature amorphous alloy material as described in claim 1, characterized in that, The Os-based high-temperature amorphous alloy composition includes Os. 46 B 38 Hf 16 Os 45 B 35 Zr 20 Os 45 B 35 V 20 Os 50 B 35 Ta 15 and Os 45 B 35 W 20 .

3. The method for preparing the Os-based high-temperature amorphous alloy material according to any one of claims 1-2, characterized in that, Includes the following steps: Step 1: According to the chemical formula Os-based high-temperature amorphous alloy... a B b M c Calculate the mass ratio of each element and weigh and mix the ingredients; element M includes at least one of Zr, Hf, V, Ta and W; a, b and c are the atomic percentages of the corresponding elements, a=39~50, b=34~44, c=12~24, and the sum of the atomic percentages of each element a+b+c=100; Step 2: Use induction melting to melt each element into a master alloy ingot; Step 3: The master alloy ingot obtained in Step 2 is heated and melted in a protective atmosphere, and Os-based high-temperature amorphous alloy strips are prepared by melt spin quenching; or the master alloy ingot obtained in Step 2 is heated and melted in a protective atmosphere, and Os-based high-temperature amorphous alloy blocks are prepared by copper mold casting.

4. The method for preparing Os-based high-temperature amorphous alloy material as described in claim 3, characterized in that, Following step 2, the process also includes rapid screening and verification of alloy components with glass-forming capabilities, specifically comprising the following steps: The master alloy ingot obtained in step 2 was cut into thin slices with a thickness of 3 mm. The surface of the thin slices was treated by laser melting and quenching technology to obtain an Os-based high-temperature amorphous alloy remelting layer. The phase analysis of the remelting layer showed that the remelting layer had broadened diffuse diffraction peaks, that is, it had a certain glass-forming ability.

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