A high-strength, lightweight, multi-component refractory green alloy and its preparation method

Abstract

The present invention discloses a high-strength, toughness, lightweight, multi-component refractory green alloy and a preparation method thereof. The multi-component high-strength, toughness, refractory green alloy is obtained by smelting recycled titanium alloy, recycled niobium alloy, and recycled zirconium alloy. By mass percentage, the recycled titanium alloy comprises 28-55wt%, the recycled niobium alloy comprises 22-35wt%, and the recycled zirconium alloy comprises 22-38wt%. Compared to currently developed refractory alloys, the high-strength, toughness, lightweight, multi-component refractory green alloy prepared by the present invention has a lower mass density, better strength-toughness matching, and a shorter preparation process. It can be applied in fields such as aerospace, nuclear energy, and chemical industry. Furthermore, the upgraded utilization of recycled alloys can effectively alleviate resource shortages and reduce production costs, contributing to the development of a circular economy.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal materials and their preparation, and specifically relates to a high-strength, tough, lightweight, multi-component refractory green alloy and a preparation method thereof. Background Art

[0002] The world produces and consumes a large amount of metal materials every year, generating a huge amount of metal waste, which places a heavy burden on resources, energy and the environment. Secondary synthesis is currently the main method for recycling metal waste to reduce the cost of alloy preparation and alleviate the burden on resources, energy and the environment. However, the performance of secondary synthesis alloys is very limited and single, usually similar to or even lower than the original alloy, and most secondary synthesis alloys are downgraded or used at the same level. As a result, the application of recycled alloys has many limitations. Therefore, if high-strength and tough green alloys can be developed, it will be of great significance to reduce the cost of alloy preparation, expand the application field of recycled alloys, and develop a green and low-carbon economy.

[0003] The new generation of high-performance structural materials requires lightweight while having excellent strength and toughness. Traditional structural materials are often based on one or two metals, and it is difficult to achieve multiple excellent properties at the same time. Multi-component alloys, as an innovative alloy design concept, break through the scope of traditional alloy design, which provides the possibility of exploring ideal performance in a vast combination space. Multi-component refractory alloys, with their excellent high-temperature performance and outstanding corrosion resistance, play an important role in modern industry. This type of alloy is mainly composed of refractory metal elements such as Nb, Zr, V, and Ti, and is widely used in aerospace, military equipment, nuclear industry, chemical industry and other fields; at the same time, a large number of "retired" alloys are also produced, with huge output; and refractory metal resources are unevenly distributed, and mining and processing are difficult, resulting in expensive raw materials and a large amount of pollutants generated during the production process, which has a serious impact on the environment. Therefore, how to develop low-cost green refractory alloys and improve their processing deformation capabilities has always been a core issue that needs to be solved urgently. Summary of the Invention

[0004] The purpose of this section is to summarize some aspects of the embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the abstract and title of this application to avoid obscuring the purpose of this section, the abstract and the title of the invention, and such simplifications or omissions should not be used to limit the scope of the present invention.

[0005] In view of the above-mentioned and / or existing problems in the prior art, such as the difficulty in mining and processing of existing refractory metals, expensive raw materials, high density, poor room temperature plasticity and difficulty in deformation processing, the present invention is proposed.

[0006] One of the purposes of the present invention is to provide a high-strength, tough, lightweight, multi-component refractory green alloy, and to provide a high-strength, tough, lightweight, multi-component refractory green alloy and a preparation method thereof, aiming to develop low-cost, green, multi-component refractory alloys to solve their problems such as poor room temperature plasticity and poor deformability.

[0007] To solve the above technical problems, the present invention provides the following technical solutions: a high-strength, tough, lightweight, multi-component refractory green alloy, a high-strength, tough, lightweight, multi-component refractory green alloy, characterized in that:

[0008] The green alloy is obtained by smelting recycled titanium alloy, recycled niobium alloy and recycled zirconium alloy as raw materials, and the recycled titanium alloy comprises 28-55wt%, the recycled niobium alloy comprises 22-35wt%, and the recycled zirconium alloy comprises 22-38wt% by weight.

[0009] Wherein, the recycled titanium alloy is Ti6Al4V alloy, the recycled niobium alloy is Nb-1Zr alloy, and the recycled zirconium alloy is Zr-2.5Nb alloy.

[0010] As a preferred solution of the high-strength, tough, lightweight, multi-component refractory green alloy of the present invention, the recycled titanium alloy is Ti6Al4V alloy, including Ti6Al4V alloy derived from waste oil drilling drill pipes, valves, pump bodies, eyeglass frames, bicycle frames, and mobile phone casings.

[0011] As a preferred solution of the high-strength, tough, lightweight, multi-component refractory green alloy of the present invention, the recycled niobium alloy is a Nb-1Zr alloy, including Nb-1Zr alloys derived from waste high-temperature nozzles, waste nuclear reactor cladding materials, and waste surgical tools.

[0012] As a preferred solution of the high-strength, tough, lightweight, multi-component refractory green alloy of the present invention, the recycled zirconium alloy is a Zr-2.5Nb alloy, including Zr-2.5Nb alloys derived from waste electronic device circuit board brackets, waste kitchen knives, waste nuclear reactor cladding materials, and waste nuclear industrial materials.

[0013] As a preferred embodiment of the high-strength, tough, lightweight, multi-component refractory green alloy of the present invention, the green alloy comprises, in atomic percentage, 38.0-60.0 at% of Ti, 14-28.0 at% of Zr, 14.0-28.0 at% of Nb, 4.0-8.0 at% of Al, 1.0-4.0 at% of V, and trace elements Fe, Ta, W, Si, Ni, Mo, and Cr, with the atomic percentage of each trace element being 0.01-2.0 at%.

[0014] As a preferred embodiment of the high-strength, toughness, lightweight, multi-component refractory green alloy of the present invention, the high-strength, toughness, lightweight, multi-component refractory green alloy has the following characteristics:

[0015] (a) The density of the alloy is 5.30-6.00 g / cm 3 ;

[0016] (b) Direct cold rolling and annealing treatment can be achieved at room temperature, with a cold rolling deformation of 20 to 100%;

[0017] (c) The tensile yield strength of the high-strength, lightweight, multi-component refractory green alloy is 800-1100 MPa at room temperature;

[0018] (d) The tensile elongation of the high-strength, tough, lightweight, multi-component refractory green alloy at room temperature is greater than 30.0%; specifically, greater than 35%; further, greater than 37%; and optimally, greater than 38.55%.

[0019] Another object of the present invention is to provide a method for preparing the high-strength, tough, lightweight, multi-component refractory green alloy as described above, comprising:

[0020] Recycle titanium alloy, niobium alloy and zirconium alloy raw materials according to mass ratio;

[0021] Use vacuum arc melting or vacuum induction melting;

[0022] By cold rolling deformation and then annealing in vacuum or protective atmosphere, a high-strength, tough, lightweight, multi-component refractory green alloy is obtained.

[0023] As a preferred embodiment of the method for preparing a high-strength, tough, lightweight, multi-component refractory green alloy of the present invention, the smelting is carried out in a vacuum or inert gas atmosphere; the smelting under vacuum has a vacuum degree of ≥1×10 -1 Pa; the smelting is carried out under an inert gas atmosphere, and the inert gas pressure in the smelting furnace is 0.000001~0.05MPa.

[0024] As a preferred solution of the method for preparing the high-strength, tough, lightweight, multi-component refractory green alloy of the present invention, wherein: the cold rolling deformation is adopted, the single-pass rolling reduction is ≤20%, and the total rolling reduction is 20% to 100%.

[0025] As a preferred embodiment of the method for preparing the high-strength, tough, lightweight, multi-component refractory green alloy of the present invention, annealing is performed in a vacuum or inert gas atmosphere at a temperature of 700-1250°C for 5-60 minutes, followed by quenching; annealing can also be further followed by aging treatment as required at a temperature of 100-600°C for 0-800 hours, followed by quenching.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] This invention introduces a multi-component alloy design concept. By recycling titanium, niobium, and zirconium alloys, a high-strength and tough multi-component refractory green alloy is developed. This not only simplifies the complex preparation process but also reduces production costs. Using recycled alloys instead of pure metals as the raw material for preparing high-strength and tough refractory alloys effectively alleviates resource constraints, reduces production costs, reduces mineral resource extraction, and reduces environmental pollution. It also helps promote the development of a circular economy and achieve sustainable development. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. Those skilled in the art can also derive other drawings based on these drawings without inventive effort. Among them:

[0029] Figure 1 Example 1Ti 44.76 Zr 25.68 Nb 22.39 Al 5.3 V 1.87 Scanning electron microscope micrograph of a high-strength, tough, lightweight, multi-component refractory green alloy after 90% homogenization cold rolling.

[0030] Figure 2 Example 1Ti 44.76 Zr 25.68 Nb 22.39 Al 5.3 V 1.87 XRD pattern of high-strength, tough, lightweight multi-component refractory green alloy after 90% homogenization treatment by cold rolling.

[0031] Figure 3 Example 1Ti 44.76 Zr 25.68 Nb 22.39 Al 5.3 V 1.87 Tensile engineering stress-engineering strain curves of a high-strength, tough, lightweight, multi-component refractory green alloy after 90% homogenization cold rolling.

[0032] Figure 4 Example 1Ti 44.76 Zr 25.68 Nb 22.39 Al 5.3 V 1.87 Tensile engineering stress-engineering strain curves of a high-strength, tough, lightweight, multi-component refractory green alloy after aging treatment.

[0033] Figure 5 Example 2Ti 49.34 Zr 21.25 Nb 21.51 Al 5.84 V 2.06 Scanning electron microscope micrograph of a high-strength, tough, lightweight, multi-component refractory green alloy after 90% homogenization cold rolling.

[0034] Figure 6 Example 2Ti 49.34 Zr 21.25 Nb 21.51 Al 5.84 V 2.06 XRD pattern of high-strength, tough, lightweight multi-component refractory green alloy after 90% homogenization treatment by cold rolling.

[0035] Figure 7 Example 2Ti 49.34 Zr 21.25 Nb 21.51 Al 5.84 V 2.06 Tensile engineering stress-engineering strain curves of a high-strength, tough, lightweight, multi-component refractory green alloy after 90% homogenization cold rolling.

[0036] Figure 8 Example 2Ti 49.34 Zr 21.25 Nb 21.51 Al 5.84 V 2.06 Tensile engineering stress-engineering strain curves of a high-strength, tough, lightweight, multi-component refractory green alloy after aging treatment.

[0037] Figure 9 Example 3Ti 53.60 Zr 17.14 Nb 20.68 Al 6.34 V 2.24 Scanning electron microscope micrograph of a high-strength, tough, lightweight, multi-component refractory green alloy after 90% homogenization cold rolling.

[0038] Figure 10 Example 3Ti 53.60 Zr 17.14 Nb 20.68 Al 6.34 V 2.24 XRD pattern of high-strength, tough, lightweight multi-component refractory green alloy after 90% homogenization treatment by cold rolling.

[0039] Figure 11 Example 3Ti 53.60 Zr 17.14 Nb 20.68 Al 6.34 V2.24 Tensile engineering stress-engineering strain curves of a high-strength, tough, lightweight, multi-component refractory green alloy after 90% homogenization cold rolling.

[0040] Figure 12 Example 3Ti 53.60 Zr 17.14 Nb 20.68 Al 6.34 V 2.24 Tensile engineering stress-engineering strain curves of a high-strength, tough, lightweight, multi-component refractory green alloy after aging treatment.

[0041] Figure 13 Example 4Ti 57.54 Zr 16.53 Nb 16.72 Al 6.81 V 2.40 Scanning electron microscope micrograph of a high-strength, tough, lightweight, multi-component refractory green alloy after 80% homogenization cold rolling.

[0042] Figure 14 Example 4Ti 57.54 Zr 16.53 Nb 16.72 Al 6.81 V 2.40 XRD pattern of high-strength, tough, lightweight multi-component refractory green alloy after 80% homogenization treatment by cold rolling.

[0043] Figure 15 Example 4Ti 57.54 Zr 16.53 Nb 16.72 Al 6.81 V 2.40 Tensile engineering stress-engineering strain curves of a high-strength, tough, lightweight, multi-component refractory green alloy after 90% homogenization cold rolling.

[0044] Figure 16 Example 4Ti 57.54 Zr 16.53 Nb 16.72 Al 6.81 V 2.40 Tensile engineering stress-engineering strain curves of a high-strength, tough, lightweight, multi-component refractory green alloy after aging treatment.

[0045] Figure 17 This is a physical picture of the alloy of comparative example 4 during the rolling deformation process. DETAILED DESCRIPTION

[0046] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.

[0047] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0048] Secondly, the term "one embodiment" or "embodiment" herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in various places throughout this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive of other embodiments.

[0049] Unless otherwise specified, the raw materials used in the examples were purchased commercially.

[0050] The recycled titanium alloy used in the embodiment of the present invention is Ti6Al4V alloy from waste oil drilling drill pipes; the recycled niobium alloy is Nb-1Zr alloy from waste surgical tools; and the recycled zirconium alloy is Zr-2.5Nb alloy from waste electronic device circuit board brackets.

[0051] The test method used in the embodiment of the present invention is:

[0052] Tensile test: The sample obtained in the embodiment was cut into a dog-bone tensile specimen of 1.62×7.5×21 mm by wire cutting, and polished on 180#, 400#, 800#, 1200#, 2000#, 3000#, and 5000# sandpaper. The polished sample was ultrasonically cleaned for 20 minutes and dried. -3 s -1 Stretching was performed at a strain rate of .

[0053] Density determination: Measured by the Archimedean displacement method. First, 8×8×8 mm block samples were uniformly cut from the as-cast sample obtained in the example. Before use, they were ultrasonically cleaned at room temperature for 20 minutes to remove surface dirt and impurities, and finally placed in a drying oven for drying. The dry weight M1 of each sample was weighed 6 times to reduce measurement error. The mass M2 of each sample in water was then weighed 6 times. Finally, the density was calculated according to the following formula:

[0054]

[0055] Where ρ0 is the temperature of water, 0.9982g / cm 3 (293K); ρ1 is the air density, 0.0012 g / cm 3 , measure three times and get the average value.

[0056] Example 1

[0057] (1) Raw material pretreatment: The recycled titanium alloy, recycled niobium alloy, and recycled zirconium alloy were polished and ultrasonically cleaned at room temperature for 30 minutes to remove surface dirt and impurities, and finally placed in a drying oven for drying;

[0058] (2) Raw material ratio: According to the chemical formula Ti 44.76 Zr 25.68 Nb 22.39 Al 5.3 V 1.87 The molar percentage and mass percentage (atomic percentage) were converted based on 100g of alloy and the materials were prepared according to the recycled alloy mass ratio of Ti6Al4V:Zr-2.5Nb:Nb-1Zr=35:35:30;

[0059] (3) Melting: The raw materials weighed in step (2) were placed into a water-cooled copper crucible in a vacuum arc furnace according to their melting points, and vacuumed to 5×10 -3 Pa, repeated three times; argon gas was filled to 0.05MPa as a protective atmosphere; before melting, an extra Ti ingot pre-placed in the furnace was melted for 2 minutes to consume the residual oxygen and nitrogen in the melting furnace. The melting current was 340A and the melting time was 180 seconds; the alloy ingot was started to be melted repeatedly for 8 times, the melting current was controlled at 400A, each melting arc should last for 8 minutes and supplemented by electromagnetic stirring technology, the current frequency was 10Hz, to ensure that the alloy was fully mixed;

[0060] (4) Casting: The uniformly smelted alloy is placed in a water-cooled copper mold of 80×30×10 mm in a vacuum arc furnace for remelting and molding. After the sample cools down, the sample is taken out. The specific operation is: vacuum to 4×10 -3 Pa, repeated three times; filled with argon to 0.04MPa as a protective atmosphere; before melting, melt the extra Ti ingot pre-placed in the furnace, the melting current is 340A, the melting time is 120 seconds; start melting the alloy ingot, repeat the melting 4 times, the melting current is controlled at 400A, and the arc should last for 8 minutes each time;

[0061] (5) Cold rolling annealing: The cast alloy was cut into 10.00 mm thick strip samples, with a single-pass rolling reduction of 10% and a total rolling reduction of 90%. The rolled sample was placed in a quartz tube and prepared for sealing. The quartz tube was first vacuumed to 1×10 -3 Pa, and then filled with argon to maintain the pressure in the tube at 0.001 MPa. After the sealing is completed, the sample is kept at 850 ° C for 10 minutes and then immediately quenched in water to obtain a high-strength, tough, lightweight, multi-component refractory green alloy. The density is measured by the Archimedean drainage method, ρ = 5.928 g / cm 3 .

[0062] Figure 1 This is a scanning electron microscope micrograph of the high-strength, tough, lightweight multi-component refractory green alloy of Example 1 after 90% cold rolling and annealing. It can be seen that the multi-component refractory green alloy can be subjected to large deformation microstructure control in the cast state. After annealing, the alloy microstructure is dense and the grain size is uniformly distributed. Statistics show that the grain size is 10.12±2.34μm.

[0063] Figure 2 is the corresponding XRD pattern of Example 1;

[0064] Figure 3 This is a tensile engineering stress-engineering strain curve of the high-strength, tough, lightweight, multi-component refractory green alloy of Example 1 after 90% homogenization treatment by cold rolling. The alloy has a yield strength of 976 MPa and a tensile elongation of 38.55% at room temperature.

[0065] The obtained high-strength, tough, lightweight, multi-component refractory green alloy was further aged at 350°C for 168 h, followed by immediate water quenching. Figure 4 This is a tensile engineering stress-engineering strain curve of the high-strength, tough, lightweight, multi-component refractory green alloy in Example 1 after annealing and further aging treatment. The strength is significantly improved after aging treatment.

[0066] Example 2

[0067] (1) Raw material pretreatment: The recycled titanium alloy, recycled niobium alloy, and recycled zirconium alloy were polished and ultrasonically cleaned at room temperature for 30 minutes to remove surface dirt and impurities, and finally placed in a drying oven for drying;

[0068] (2) Raw material ratio: According to the chemical formula Ti 49.34 Zr 21.25 Nb 21.51 Al 5.84 V 2.06 The molar percentage and mass percentage of (atomic percentage) are converted based on 100g of alloy, and the ingredients are prepared according to the recycled alloy mass ratio Ti6Al4V:Zr-2.5Nb:Nb-1Zr=40:30:30;

[0069] (3) Melting: Place the raw materials weighed in step 2 into a water-cooled copper crucible in a vacuum arc furnace according to their melting points, and evacuate to 5×10 -3Pa, repeated three times; argon gas was filled to 0.05MPa as a protective atmosphere; before melting, an extra Ti ingot pre-placed in the furnace was melted for 2 minutes to consume the residual oxygen and nitrogen in the melting furnace. The melting current was 340A and the melting time was 180 seconds; the alloy ingot was started to be melted repeatedly for 8 times, the melting current was controlled at 400A, each melting arc should last for 8 minutes and supplemented by electromagnetic stirring technology, the current frequency was 10Hz, to ensure that the alloy was fully mixed;

[0070] (4) Casting: The uniformly smelted alloy is placed in a water-cooled copper mold of 80×30×10 mm in a vacuum arc furnace for remelting and molding. After the sample cools down, the sample is taken out. The specific operation is: vacuum to 4×10 -3 Pa, repeated three times; filled with argon to 0.04MPa as a protective atmosphere; before melting, melt the extra Ti ingot pre-placed in the furnace, the melting current is 340A, the melting time is 120 seconds; start melting the alloy ingot, repeat the melting 4 times, the melting current is controlled at 400A, and the arc should last for 8 minutes each time;

[0071] (5) Cold rolling annealing: The cast alloy was cut into 10.00 mm thick strip samples, with a single-pass rolling reduction of 10% and a total rolling reduction of 90%. The rolled sample was placed in a quartz tube and prepared for sealing. The quartz tube was first vacuumed to 1×10 -3 Pa, and then filled with argon to maintain the pressure in the tube at 0.001 MPa. After the sealing is completed, the sample is kept at 850 ° C for 10 minutes and then immediately quenched in water to obtain a high-strength, tough, lightweight, multi-component refractory green alloy. The density is measured by the Archimedean drainage method, ρ = 5.798 g / cm 3 .

[0072] Figure 5 The scanning electron microscope micrograph of Example 2 is obtained after the high-strength, tough, lightweight, multi-component refractory green alloy is kept at 850°C for 10 minutes and then immediately water quenched. It can be seen that after the cold rolling and annealing treatment, the alloy microstructure is dense, and the grains are relatively large and evenly distributed.

[0073] Figure 6 This is the corresponding XRD pattern of Example 2.

[0074] Figure 7 This is a homogeneous tensile engineering stress-engineering strain curve of the high-strength, tough, lightweight, multi-component refractory green alloy of Example 2. After vacuum annealing, the alloy exhibits a tensile yield strength of 942 MPa and a tensile elongation of 37.3%.

[0075] The obtained high-strength, tough, lightweight, multi-component refractory green alloy was further aged at 350°C for 168 h, followed by immediate water quenching. Figure 8This is the engineering stress-engineering strain curve of the high-strength, tough, lightweight, multi-component refractory green alloy after aging in Example 2. The strength and plasticity of the alloy are simultaneously improved.

[0076] Example 3

[0077] (1) Raw material pretreatment: The recycled titanium alloy, recycled niobium alloy, and recycled zirconium alloy were polished and ultrasonically cleaned at room temperature for 30 minutes to remove surface dirt and impurities, and finally placed in a drying oven for drying;

[0078] (2) Raw material ratio: According to the chemical formula Ti 53.60 Zr 17.14 Nb 20.68 Al 6.34 V 2.24 The molar percentage and mass percentage of (atomic percentage) are converted based on 100g of alloy, and the ingredients are prepared according to the recycled alloy mass ratio Ti6Al4V:Zr-2.5Nb:Nb-1Zr=45:25:30;

[0079] (3) Melting: according to the melting point, the raw materials weighed in step 2 are placed in a water-cooled copper crucible of a vacuum arc furnace in sequence, and the vacuum is evacuated to 5×10-3Pa, and repeated three times; argon is filled to 0.05MPa as a protective atmosphere; before melting, the extra Ti ingots pre-placed in the furnace are melted for 2 minutes to consume the residual oxygen and nitrogen in the melting furnace, the melting current is 340A, and the melting time is 180 seconds; start melting the alloy ingot, and melt it repeatedly for 8 times, the melting current is controlled at 400A, each melting arc should last for 8 minutes and supplemented by electromagnetic stirring technology, the current frequency is 10Hz, to ensure that the alloy is fully mixed;

[0080] (4) Casting: The uniformly melted alloy was placed in a water-cooled copper mold of 80×30×10mm in a vacuum arc furnace for remelting and shaping. After the sample cooled, the sample was taken out. The specific operation was as follows: vacuuming to 4×10-3Pa, repeated three times; filling with argon to 0.04MPa as a protective atmosphere; before melting, the extra Ti ingot pre-placed in the furnace was melted, the melting current was 340A, and the melting time was 120 seconds; the alloy ingot was melted, and the melting was repeated 4 times, the melting current was controlled at 400A, and the arc should last for 8 minutes each time;

[0081] (5) Cold rolling annealing: The cast alloy was cut into 10.00 mm thick strip samples, with a single-pass rolling reduction of 10% and a total rolling reduction of 90%. The rolled sample was placed in a quartz tube and prepared for sealing. The quartz tube was first vacuumed to 1×10 -3Pa, and then filled with argon to maintain the pressure in the tube at 0.001 MPa. After the sealing is completed, the sample is kept at 850 ° C for 10 minutes and then immediately quenched in water to obtain a high-strength, tough, lightweight, multi-component refractory green alloy. The density is measured by the Archimedean drainage method, ρ = 5.675 g / cm 3 .

[0082] Figure 9 The high-strength, tough, lightweight, multi-component refractory green alloy of Example 3 was cold-rolled by 90%, kept at 850°C for 10 minutes, and then immediately water-quenched to obtain a scanning electron microscope micrograph. It can be seen that after the cold-rolling and annealing treatment, equiaxed grains are uniformly distributed.

[0083] Figure 10 This is the corresponding XRD pattern of Example 3.

[0084] Figure 11 This is a homogeneous tensile engineering stress-engineering strain curve of Example 3 of a high-strength, tough, lightweight, multi-component refractory green alloy. The alloy exhibits a tensile yield strength of 913 MPa and a room temperature tensile elongation of 37.3%.

[0085] The obtained high-strength, tough, lightweight, multi-component refractory green alloy was further aged at 350°C for 168 h, followed by immediate water quenching. Figure 12 This is a tensile engineering stress-engineering strain curve of the high-strength, tough, lightweight, multi-component refractory green alloy after aging in Example 3, and the strength of the alloy is significantly improved.

[0086] Example 4

[0087] (1) Raw material pretreatment: The recycled titanium alloy, recycled niobium alloy, and recycled zirconium alloy were polished and ultrasonically cleaned at room temperature for 30 minutes to remove surface dirt and impurities, and finally placed in a drying oven for drying;

[0088] (2) Raw material ratio: According to the chemical formula Ti 57.54 Zr 16.53 Nb 16.72 Al 6.81 V 2.40 The molar percentage and mass percentage of (atomic percentage) are converted based on 100g of alloy, and the ingredients are prepared according to the recycled alloy mass ratio Ti6Al4V:Zr-2.5Nb:Nb-1Zr=50:25:25;

[0089] (3) Melting: Place the raw materials weighed in step 2 into a water-cooled copper crucible in a vacuum arc furnace according to their melting points, and evacuate to 5×10 -3Pa, repeated three times; argon gas was filled to 0.05MPa as a protective atmosphere; before melting, an extra Ti ingot pre-placed in the furnace was melted for 2 minutes to consume the residual oxygen and nitrogen in the melting furnace. The melting current was 340A and the melting time was 180 seconds; the alloy ingot was started to be melted repeatedly for 8 times, the melting current was controlled at 400A, each melting arc should last for 8 minutes and supplemented by electromagnetic stirring technology, the current frequency was 10Hz, to ensure that the alloy was fully mixed;

[0090] (4) Casting: The uniformly melted alloy was placed in a water-cooled copper mold of 80×30×10mm in a vacuum arc furnace for remelting and shaping. After the sample cooled, the sample was taken out. The specific operation was as follows: vacuuming to 4×10-3Pa, repeated three times; filling with argon to 0.04MPa as a protective atmosphere; before melting, the extra Ti ingot pre-placed in the furnace was melted, the melting current was 340A, and the melting time was 120 seconds; the alloy ingot was melted, and the melting was repeated 4 times, the melting current was controlled at 400A, and the arc should last for 8 minutes each time;

[0091] (5) Cold rolling annealing: The cast alloy was cut into 10.00 mm thick strip samples, with a single-pass rolling reduction of 10% and a total rolling reduction of 90%. The rolled sample was placed in a quartz tube and prepared for sealing. The quartz tube was first vacuumed to 1×10 -3 Pa, and then filled with argon to maintain the pressure in the tube at 0.001 MPa. After the sealing is completed, the sample is kept at 850 ° C for 10 minutes and then immediately quenched in water to obtain a high-strength, tough, lightweight, multi-component refractory green alloy. The density is measured by the Archimedean drainage method, ρ = 5.501 g / cm 3 .

[0092] Figure 13 The high-strength, tough, lightweight, multi-component refractory green alloy of Example 4 was cold-rolled by 80%, kept at 850°C for 10 minutes, and then immediately water-quenched to obtain a scanning electron microscope micrograph. It can be seen that after the cold-rolling and annealing treatment, equiaxed grains are uniformly distributed.

[0093] Figure 14 This is the corresponding XRD pattern of Example 4.

[0094] Figure 15 This is a homogeneous tensile engineering stress-engineering strain curve of the high-strength, tough, lightweight, multi-component refractory green alloy of Example 4. The alloy exhibits a tensile yield strength of 904 MPa and a room temperature tensile elongation of 38.4%.

[0095] The obtained high-strength, tough, lightweight, multi-component refractory green alloy was further aged at 350°C for 168 h, followed by immediate water quenching. Figure 16This is a tensile engineering stress-engineering strain curve of the high-strength, tough, lightweight, multi-component refractory green alloy of Example 4 after aging treatment, and the strength of the alloy is further improved.

[0096] Comparative Example 1

[0097] Ti6Al4V alloy

[0098] According to the literature Zhao R, Chen C, Shuai, Sansan Hu, Tao Fautrelle, Yves Liao, Hanlin Lu, Jian Wang, Jiang Ren, Zhongming. Enhanced mechanical properties of Ti6Al4V alloy fabricated by laser additive manufacturing under static magnetic field [J]. materials research letters, 2022, 10 (8): 530-538., it can be seen that the strength of Ti6Al4V alloy is relatively high at around 800 MPa, but the plasticity is relatively low, only 14%.

[0099] Comparative Example 2

[0100] Zr-2.5Nb alloy

[0101] According to the literature Rodriguez-Espinoza, BL, et al."High-strength low-modulusbiocompatible Nb-1Zr alloy processed by accumulative roll bonding." Materials Science & Engineering, A. Structural Materials: Properties, Misrostructure and Processing 797-(2020): 797., it can be seen that the strength of Zr-2.5Nb alloy is about 500MPa and the plasticity is about 20%.

[0102] Comparative Example 3

[0103] Nb-1Zr alloy

[0104] According to the literature (Yu T, Ye P, Chang Z. The Oxidation Behavior of Zr-2.5Nb (wt%) Alloy in Dry Air [J]. High Temperature Corrosion of Materials, 2023. DOI: 10.1007 / s11085-023-10149-3), the properties of Nb-1Zr alloys vary depending on the alloy preparation method, heat treatment conditions, and added trace elements. Generally speaking, the yield strength of Nb-1Zr alloys ranges from 250 to 450 MPa, and the elongation ranges from 10 to 30%.

[0105] Comparative Example 4

[0106] Comparative Example 4 is based on Example 1. The alloy is converted based on 100g of alloy and the recycled alloy mass ratio is Ti6Al4V: Zr-2.5Nb: Nb-1Zr = 25:25:50. When the pressure in the vacuum arc furnace is pumped to 5×10 -3 After Pa, inert gas was filled in, and under the protection of inert gas, the alloy sample was repeatedly turned over and smelted 6 times, and cast to obtain a casting billet. Other conditions were the same as those in Example 1, that is, the alloy in Comparative Example 4 was obtained.

[0107] Figure 17 This is the macroscopic morphology of the comparative alloy after rolling. The alloy cracked during rolling deformation.

[0108] The present invention develops a multi-component refractory green alloy with high strength and toughness by recycling titanium alloy, niobium alloy and zirconium alloy. The room temperature tensile elongation reaches 40.0%, and the room temperature tensile yield strength is 800-1000 MPa. The alloy density is ρ=5.50-6.00 g / cm 3 Direct cold rolling-annealing treatment can be achieved at room temperature to achieve organizational control, which is beneficial to deformation processing and can realize the preparation of large-size samples; at the same time, it can simplify the cumbersome preparation process, reduce the preparation cost, effectively alleviate the resource shortage problem to reduce production costs, reduce the mining of mineral resources to reduce environmental pollution.

[0109] The high-strength, toughness, lightweight, multi-component refractory green alloy provided by the present invention has the following characteristics in terms of component matching: compared with general multi-component alloys, the alloy uses recycled alloys instead of pure metal particles as raw materials, which can significantly reduce the cost of alloy preparation; at the same time, it reduces the pollution to the environment caused by refining pure metals, which is conducive to the development of green multi-component alloys. In terms of alloy performance, it has good strength and plasticity matching while achieving lightweight; the developed high-strength, toughness, lightweight, and multi-component refractory green alloy has high specific strength, low density, high oxidation resistance, and good creep resistance. It can be used for heat-resistant components in aviation, aerospace, and automotive industries, and has excellent room temperature processing deformation capabilities. In particular, for the forming of complex-shaped thin-walled components, it can obtain precise and complex components with no or nearly no margin, greatly reducing metal loss, improving material utilization, reducing a large amount of machining, and greatly reducing production costs.

[0110] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. A high-strength, lightweight, multi-component refractory green alloy, characterized by: The green alloy is obtained by smelting recycled titanium alloy, recycled niobium alloy and recycled zirconium alloy as raw materials, wherein, by mass percentage, the recycled titanium alloy comprises 28-55 wt%, the recycled niobium alloy comprises 22-35 wt%, and the recycled zirconium alloy comprises 22-38 wt%. Wherein, the recycled titanium alloy is Ti6Al4V alloy, the recycled niobium alloy is Nb-1Zr alloy, and the recycled zirconium alloy is Zr-2.5Nb alloy; The green alloy comprises, by atomic percentage, 38.0-60.0 at%, of Ti, 14-28.0 at%, of Zr, 14.0-28.0 at%, of Nb, 4.0-8.0 at%, of Al, 1.0-4.0 at%, of V, and trace elements of Fe, Ta, W, Si, Ni, Mo, and Cr, wherein the atomic percentage of each trace element is 0.01-2.0 at%. The high-strength, tough, lightweight, multi-component refractory green alloy has the following characteristics: (a) The density of the alloy is 5.30~6.00g / cm 3 ; (b) Direct cold rolling-annealing treatment can be achieved at room temperature, with a cold rolling deformation of 20~100%; (c) The tensile yield strength of the high-strength, tough, lightweight, multi-component refractory green alloy at room temperature is 800-1100 MPa; (d) The tensile elongation of the high-strength, tough, lightweight, multi-component refractory green alloy at room temperature is above 30.0%.

2. The high-strength, toughness, lightweight, multi-component refractory green alloy according to claim 1, characterized in that: The recycled titanium alloy includes Ti6Al4V alloy derived from waste oil drilling pipes, valves, pump bodies, eyeglass frames, bicycle frames, and mobile phone casings.

3. The high-strength, toughness, lightweight, multi-component refractory green alloy according to claim 1, characterized in that: The recycled niobium alloy includes Nb-1Zr alloy from waste high-temperature nozzles, waste nuclear reactor cladding materials, and waste surgical tools.

4. The high-strength, toughness, lightweight, multi-component refractory green alloy according to claim 1, characterized in that: The recycled zirconium alloy includes Zr-2.5Nb alloy derived from waste electronic device circuit board brackets, waste kitchen knives, waste nuclear reactor cladding materials, and waste nuclear industry materials.

5. The method for preparing a high-strength, tough, lightweight, multi-component refractory green alloy according to any one of claims 1 to 4, characterized in that: include, Recycle titanium alloy, niobium alloy and zirconium alloy raw materials according to mass ratio; Use vacuum arc melting or vacuum induction melting; By cold rolling deformation and then annealing in vacuum or protective atmosphere, a high-strength, tough, lightweight, multi-component refractory green alloy is obtained.

6. The method for preparing a high-strength, tough, lightweight, multi-component refractory green alloy according to claim 5, wherein: The cold rolling deformation is adopted, the single-pass rolling reduction is ≤20%, and the total rolling reduction is 20%~100%.

7. The method for preparing a high-strength, tough, lightweight, multi-component refractory green alloy according to claim 6, wherein: Annealing treatment is carried out in a vacuum or inert gas atmosphere at an annealing temperature of 700-1250°C for 5-60 min, followed by quenching. Further aging treatment can also be carried out after annealing as needed at an aging temperature of 100-600°C for 0-800 h, followed by quenching.

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