A Ti-Zr-V lightweight refractory multi-principal-element eutectic alloy, its preparation method and applications

Abstract

This invention provides a Ti-Zr-V lightweight refractory multi-principal-element eutectic alloy, its preparation method, and its applications. The Ti-Zr-V lightweight refractory multi-principal-element eutectic alloy has the general formula Ti a Zr b V c 14% of them

Description

Technical Field

[0001] The present invention relates to the technology of high-entropy alloys, and particularly to a Ti-Zr-V series lightweight refractory multi-principal element eutectic alloy, its preparation method and uses. Background Art

[0002] Aero-engines are national key equipment and an important manifestation of a country's scientific and technological strength. The service environment of aviation components is extremely harsh, posing higher requirements for the currently under-research metallic materials. Since 2010, refractory high-entropy alloys have received extensive attention due to their excellent mechanical properties and high-temperature stability, and are expected to become candidate materials for next-generation aerospace components. Refractory high-entropy alloys generally consist mainly of elements with melting points above 1500 °C, which greatly limits the casting conditions of refractory high-entropy alloys. Since the concept of eutectic high-entropy alloys was proposed by Professor Lu Yiping of Dalian University of Technology in 2014, the eutectic high-entropy alloy system has developed rapidly. For the currently reported eutectic high-entropy alloys, they mainly consist of FCC + B2 phase structures or FCC + BCC phase structures, while less research has been carried out on eutectic refractory high-entropy alloys composed of BCC1 + BCC2 phase structures. In addition, high density is another huge challenge currently faced by refractory high-entropy alloys. Summary of the Invention

[0003] The object of the present invention is to propose a Ti-Zr-V series lightweight refractory multi-principal element eutectic alloy in view of the problems of high density and poor casting formability of the above-mentioned refractory high-entropy alloys. This alloy combines the design concepts of refractory high-entropy alloys and eutectic alloys, combines the BCC1 solid solution enriched with Ti and V elements and the BCC2 solid solution enriched with Ti and Zr elements, and exhibits a lower density and excellent casting fluidity. The lightweight refractory multi-principal element eutectic alloy provided by the present invention has both excellent casting formability and a lower density, and is expected to realize the engineering application of multi-principal element refractory alloys.

[0004] To achieve the above object, the technical solution adopted by the present invention is: a Ti-Zr-V series lightweight refractory multi-principal element eutectic alloy, whose general formula is Ti a Zr b V c , where 14% < a < 25%, 48% < b < 55%, 26% < c < 31%, and a + b + c = 100, and a, b, and c respectively correspond to the molar percentages of the elements.

[0005] Further, the general formula Ti a Zr b V c satisfies: 14.5% < a < 25%, 48.5% < b < 55%, 27% < c < 30.5%.

[0006] Furthermore, the Ti-Zr-V lightweight refractory multi-principal eutectic alloy has a BCC1 and BCC2 dual-phase structure.

[0007] Furthermore, the density of the Ti-Zr-V system lightweight refractory multi-principal eutectic alloy is 6.1 g / cm³. 3 and below.

[0008] Furthermore, the density of the Ti-Zr-V lightweight refractory multi-principal-element eutectic alloy is 5.5-6.1 g / cm³. 3 .

[0009] Another objective of this invention discloses a method for preparing a Ti-Zr-V system lightweight refractory multi-principal-element eutectic alloy, comprising the following steps:

[0010] Step 1, Grinding: Grind the surface of the metallic elemental raw materials Ti, Zr, and V to remove the oxide scale and impurities on the surface;

[0011] Step 2, Cleaning: Place the polished metal elemental raw materials Ti, Zr, and V into separate containers, pour in ethanol, clean them with an ultrasonic cleaner, and after they are fully dried, put them into sealed bags for later use.

[0012] Step 3, Ingredients: Weigh each component according to the general formula;

[0013] Step 4, Smelting: Place the elemental metals Ti, Zr, and V into a copper crucible in a vacuum arc melting furnace, and place the prepared Ti ingot in another copper crucible; close the furnace door, evacuate, and fill with high-purity argon; after high-frequency arc ignition, first melt the Ti ingot, then melt the elemental metals in the copper crucible. After complete melting, turn off the current and then cool the furnace; repeat this step for the alloy raw materials; after melting, open the furnace door and take out the sample after the alloy ingot has completely cooled to obtain a Ti-Zr-V lightweight refractory multi-principal eutectic alloy.

[0014] Furthermore, when selecting elemental raw materials, the purity of the elemental metal raw materials Ti, Zr, and V is greater than or equal to 99.95 wt.%.

[0015] Furthermore, during ultrasonic cleaning in step 2, the metallic raw material should be cleaned at least 3 to 4 times, with each cleaning session lasting at least 6 to 10 minutes.

[0016] Furthermore, when weighing the elemental raw materials, the weighing error is ±0.001g.

[0017] Furthermore, in step 4, the vacuum level of the electric arc furnace is evacuated to 5 × 10⁻⁶. -3 When the pressure is below Pa, the high-purity argon gas is filled in the range of -0.05 to -0.03 Pa.

[0018] Furthermore, when smelting Ti ingots, the process involves 3 to 6 smeltings, each lasting 60 to 70 seconds, to remove excess oxygen as much as possible; when smelting alloy raw materials, the process involves repeated turning and smelting 8 to 10 times, each lasting 100 to 120 seconds, to obtain a uniform microstructure.

[0019] Furthermore, when smelting alloy ingots, the current is 350-600A, and the molten state is maintained for 1-2 minutes.

[0020] Another objective of this invention is to disclose the application of a Ti-Zr-V lightweight refractory multi-principal eutectic alloy in the field of aerospace components.

[0021] The present invention relates to a Ti-Zr-V system lightweight refractory multi-principal-element eutectic alloy, its preparation method, and its applications, which have the following advantages compared with existing technologies:

[0022] 1) This invention realizes the eutectic structure design of a Ti-Zr-V system lightweight refractory multi-principal eutectic alloy. By adjusting the ratio of principal components Ti, Zr and V, a refractory multi-principal alloy with a eutectic structure can be obtained.

[0023] 2) The Ti-Zr-V system lightweight refractory multi-principal-element eutectic alloy of this invention not only exhibits low density (5.5-6.1 g / cm³), but also... 3 Furthermore, the selected Ti, Zr, and V elements are beneficial to improving the alloy's corrosion resistance, wear resistance, and high-temperature stability, thus showing potential application prospects in the field of engineering structures.

[0024] 3) The Ti-Zr-V system lightweight refractory multi-principal element eutectic alloy of the present invention is composed of BCC1 (enriched with Ti and V elements) and BCC2 (enriched with Ti and Zr elements);

[0025] 4) Compared with traditional refractory multi-principal eutectic alloys, the Ti-Zr-V series lightweight refractory multi-principal eutectic alloy of the present invention has the advantages of low melting point and good fluidity. It can be used to cast various large-size complex precision components and can achieve one-piece molding.

[0026] In summary, the lightweight refractory multi-principal eutectic alloy of this invention exhibits low density and excellent casting fluidity through the combination of BCC1 solid solution enriched with Ti and V elements and BCC2 solid solution enriched with Ti and Zr elements. It also exhibits excellent comprehensive mechanical properties, thus showing potential application prospects in aerospace components. Attached Figure Description

[0027] Figure 1 Example 1Ti 14.5 Zr 55 V 30.5 Microstructure of lightweight, refractory, multi-principal-element eutectic alloy in the as-cast state;

[0028] Figure 2 Example 1Ti 14.5 Zr 55 V 30.5 XRD patterns of lightweight, refractory, multi-principal-element eutectic alloys in the as-cast state;

[0029] Figure 3 Example 1Ti 14.5 Zr 55 V 30.5 Stress-strain curves of lightweight, refractory, multi-principal-element eutectic alloys under as-cast conditions at room temperature under compression.

[0030] Figure 4 Example 2Ti 24.4 Zr 48.6 V 27 XRD patterns of lightweight, refractory, multi-principal-element hypereutectic alloys in the as-cast state;

[0031] Figure 5 Example 2Ti 24.4 Zr 48.6 V 27 Stress-strain curves of room temperature tensile engineering for lightweight, refractory, multi-principal-element hypereutectic alloys in the as-cast state. Detailed Implementation

[0032] The present invention will be further described below with reference to embodiments. The description of the technical features described below is based on representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:

[0033] Unless otherwise stated, all units used in this specification are international standard units, and all numerical values ​​and ranges appearing in this invention should be understood to include systematic errors that are unavoidable in industrial production.

[0034] In this specification, the range of values ​​referred to as "value A to value B" refers to the range including the endpoint values ​​A and B.

[0035] In this specification, the numerical range indicated by "above" or "below" refers to the numerical range that includes the stated number.

[0036] In this specification, the word "may" has two meanings: to perform a certain process and not to perform a certain process.

[0037] In this specification, the terms "optional" or "optional" are used to indicate the use or omission of certain substances, components, procedures, application conditions, etc.

[0038] In this instruction manual, when "room temperature" or "room temperature" is used, the temperature can be 15-25℃.

[0039] Unless otherwise specified, all reagents or instruments used in this instruction manual are commercially available products.

[0040] Example 1

[0041] This embodiment discloses a lightweight, refractory, multi-principal-element eutectic alloy with the general formula Ti. 14.5 Zr 55 V 30.5 The specific preparation method is as follows:

[0042] Step 1, Grinding: Use different grades (80#, 240# and 600#) of SiC sandpaper to grind the surface of the metallic elemental raw materials Ti, Zr and V (purity of 99.95wt.%) to remove the oxide scale and impurities on the surface.

[0043] Step 2, Cleaning: Place the polished elemental metals Ti, Zr, and V into separate beakers, pour in alcohol, and perform ultrasonic cleaning. During ultrasonic cleaning, the elemental metals are cleaned three times, with each cleaning cycle lasting 8 minutes. After thorough drying, place them in sealed bags for later use.

[0044] Step 3, Batching: Calculate the mass percentage based on the molar percentage of the lightweight refractory multi-principal-element eutectic alloy. Using a total mass of 50g for each alloy ingot, weigh each element using an electronic balance. The weighed masses of Ti, Zr, and V are 7.206g, 27.460g, and 15.334g, respectively, with a weighing error of ±0.001g.

[0045] Step 4, Melting: Place the prepared raw materials into a copper crucible in a vacuum arc furnace, and place the pre-prepared Ti ingots into another copper crucible. Close the furnace door and evacuate to 4.5 × 10⁻⁶. -3 After Pa, high-purity argon gas is introduced in reverse to -0.05 Pa. After arc ignition, the Ti ingot is first melted three times, each time for 60 seconds, to remove excess oxygen as much as possible. Then, the mixed raw materials are melted, repeatedly turned and melted nine times, each time for 120 seconds, to obtain a uniform microstructure, ultimately yielding Ti. 14.5 Zr 55 V 30.5 Lightweight, refractory, multi-principal-element eutectic alloy.

[0046] Figure 1 Example 1Ti 14.5 Zr 55 V 30.5 The microstructure of the lightweight, refractory, multi-principal-element eutectic alloy in the as-cast state shows that the prepared alloy has typical eutectic microstructure characteristics.

[0047] Figure 2Example 1Ti 14.5 Zr 55 V 30.5 XRD patterns of lightweight, refractory, multi-principal-element eutectic alloys in the as-cast state, as seen in the Ti example. 14.5 Zr 55 V 30.5 The lightweight, refractory, multi-principal-element eutectic alloy is composed of a BCC1+BCC2 phase structure;

[0048] Figure 3 Example 1Ti 14.5 Zr 55 V 30.5 The room temperature compressive stress-strain curves of the as-cast lightweight refractory multi-principal-element eutectic alloy Ti in this embodiment are shown. 14.5 Zr 55 V 30.5 The lightweight refractory multi-principal eutectic alloy exhibits a compressive strength of 1400 MPa and a fracture plasticity of 8.2%, demonstrating superior mechanical properties.

[0049] Example 2

[0050] This embodiment discloses a lightweight, refractory, multi-principal-element hypoeutectic alloy with the general formula Ti. 24.4 Zr 48.6 V 27 The specific preparation method is as follows:

[0051] Step 1, Grinding: Use different grades (80#, 240# and 600#) of SiC sandpaper to grind the surface of the metallic elemental raw materials Ti, Zr and V (purity of 99.95wt.%) to remove the oxide scale and impurities on the surface.

[0052] Step 2, Cleaning: Place the polished elemental metals Ti, Zr, and V into separate beakers, pour in alcohol, and perform ultrasonic cleaning. During ultrasonic cleaning, the elemental metals are cleaned three times, with each cleaning cycle lasting 8 minutes. After thorough drying, place them in sealed bags for later use.

[0053] Step 3, Batching: Calculate the mass percentage based on the molar percentage of the lightweight refractory multi-principal-element eutectic alloy. Using a total mass of 50g for each alloy ingot, weigh each element using an electronic balance 7. The weighed masses of Ti, Zr, and V are 12.597g, 24.001g, and 13.402g, respectively, with a weighing error of ±0.001g.

[0054] Step 4, Melting: Place the prepared raw materials into a copper crucible in a vacuum arc furnace, and place the pre-prepared Ti ingots into another copper crucible. Close the furnace door and evacuate to 4.5 × 10⁻⁶. -3After Pa, high-purity argon gas is introduced in reverse to -0.05 Pa. After arc ignition, the Ti ingot is first melted three times, each time for 60 seconds, to remove excess oxygen as much as possible. Then, the mixed raw materials are melted, repeatedly turned and melted nine times, each time for 120 seconds, to obtain a uniform microstructure, ultimately yielding Ti. 24.4 Zr 48.6 V 27 Lightweight, refractory, multi-principal-element eutectic alloy.

[0055] Figure 4 Example 2Ti 24.4 Zr 48.6 V 27 XRD patterns of lightweight, refractory, multi-principal-element hypereutectic alloys in the as-cast state, as seen in Example Ti. 24.4 Zr 48.6 V 27 Lightweight, refractory, multi-principal-element hypereutectic alloys are composed of a BCC1+BCC2 phase structure;

[0056] Figure 5 Example 2Ti 24.4 Zr 48.6 V 27 The room temperature tensile stress-strain curves of the as-cast lightweight refractory multi-principal-element hypereutectic alloy Ti in this embodiment are shown. 24.4 Zr 48.6 V 27 The lightweight refractory multi-principal-element hypereutectic alloy exhibits a tensile strength of 885 MPa and a fracture plasticity of 9.5%, demonstrating superior mechanical properties.

[0057] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A Ti-Zr-V system lightweight refractory multi-principal-element eutectic alloy, characterized in that, Its general formula is Ti a Zr b V c , where 14% < a < 25%, 48% < b < 55%, 26% < c < 31%, and a + b + c = 100, and a, b, and c respectively correspond to the molar percentages of the elements; The Ti-Zr-V series lightweight refractory multi-principal eutectic alloy has a BCC1 and BCC2 dual-phase structure.

2. The Ti-Zr-V system lightweight refractory multi-principal-element eutectic alloy according to claim 1, characterized in that, The density of the Ti-Zr-V system lightweight refractory multi-principal eutectic alloy is 6.1 g / cm³. 3 the following.

3. A method for preparing a Ti-Zr-V lightweight refractory multi-principal-element eutectic alloy according to any one of claims 1-2, characterized in that, Includes the following steps: Step 1, Grinding: Grind the surface of the metallic elemental raw materials Ti, Zr, and V to remove the oxide scale and impurities on the surface; Step 2, Cleaning: Place the polished metal elemental raw materials Ti, Zr, and V into separate containers, pour in ethanol, clean them with an ultrasonic cleaner, and after they are fully dried, put them into sealed bags for later use. Step 3, Ingredients: Weigh each component according to the general formula; Step 4, Smelting: Place the elemental metals Ti, Zr, and V into a copper crucible in a vacuum arc melting furnace, and place the prepared Ti ingot in another copper crucible; close the furnace door, evacuate, and fill with high-purity argon; after high-frequency arc ignition, first melt the Ti ingot, then melt the elemental metals in the copper crucible. After complete melting, turn off the current and then cool the furnace; repeat this step for the alloy raw materials; after melting, open the furnace door and take out the sample after the alloy ingot has completely cooled to obtain a Ti-Zr-V lightweight refractory multi-principal eutectic alloy.

4. The method for preparing the Ti-Zr-V system lightweight refractory multi-principal-element eutectic alloy according to claim 3, characterized in that, The purity of the metallic elemental raw materials Ti, Zr, and V is greater than or equal to 99.95 wt.%.

5. The method for preparing the Ti-Zr-V system lightweight refractory multi-principal-element eutectic alloy according to claim 3, characterized in that, During ultrasonic cleaning in step 2, the metallic raw material should be cleaned at least 3 to 4 times, with each cleaning session lasting at least 6 to 10 minutes.

6. The method for preparing the Ti-Zr-V system lightweight refractory multi-principal-element eutectic alloy according to claim 3, characterized in that, Step 4: Evacuate the electric arc furnace to a vacuum level of 5×10⁻⁶. -3 Below Pa, high-purity argon gas is introduced at a pressure of -0.05 to -0.03 Pa.

7. The method for preparing the Ti-Zr-V system lightweight refractory multi-principal-element eutectic alloy according to claim 3, characterized in that, When smelting Ti ingots, smelt 3 to 6 times, each smelting time is 60 to 70 seconds; when smelting alloy raw materials, smelt repeatedly by turning over 8 to 10 times, each smelting time is 100 to 120 seconds.

8. The method for preparing the Ti-Zr-V system lightweight refractory multi-principal-element eutectic alloy according to claim 3, characterized in that, When smelting alloy ingots, the current is 350~600 A, and the molten state is maintained for 1-2 minutes.

9. The use of the Ti-Zr-V lightweight refractory multi-principal eutectic alloy according to any one of claims 1-2 in the field of aerospace components.

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