Method for enhancing high plasticity of Zr-based amorphous alloy and Zr-based amorphous alloy

Abstract

The invention provides a method for enhancing the strong plasticity of a Zr-based amorphous alloy and the Zr-based amorphous alloy. According to the method, structural optimization of the atomic scale of the Zr-based amorphous alloy can be caused, stress concentration in the deformation process can be restrained, nucleation, reproduction and interaction of a shear band are promoted, the plasticity and breaking strength of the Zr-based amorphous alloy are improved, the plasticity of the Zr-based amorphous alloy subjected to heat treatment can reach 9.36%, the breaking strength can reach 2289 MPa, and the thermal conductivity of the Zr-based amorphous alloy can be improved. Compared with Zr-based amorphous alloy which is not subjected to heat treatment, the plasticity and the breaking strength of the Zr-based amorphous alloy can be improved. Therefore, the method provided by the invention is helpful to solve the problem of limited application caused by brittleness of the Zr-based amorphous alloy, and is expected to expand the application prospect of the amorphous alloy.

Description

Technical Field

[0001] The invention belongs to the technical field of amorphous alloy preparation, and specifically relates to a method for enhancing the strength and plasticity of a Zr-based amorphous alloy and a Zr-based amorphous alloy. Background Art

[0002] Compared with conventional crystalline alloys, amorphous alloys, as a new type of material, show excellent strength, elastic limit, hardness and excellent corrosion resistance, and have attracted great attention in the field of materials science. The atomic arrangement of amorphous alloys shows the characteristics of short-range order and long-range disorder, which avoids common defects such as grain boundaries and dislocations in crystalline alloys, thus giving amorphous alloys more superior mechanical properties. However, the wide application of amorphous alloys is limited by their limited plastic deformation capacity at room temperature. This defect stems from the lack of microstructures inside that can effectively bear plastic deformation. Especially after the yield point, amorphous alloys usually suffer sudden and catastrophic fractures, which is mainly attributed to the fact that their plastic strain is highly concentrated in individual or a small number of shear bands. Therefore, exploring and improving the plastic deformation capacity of amorphous alloys is of vital importance to broadening their application areas and improving the overall performance of materials. Summary of the invention

[0003] In view of this, the object of the present invention is to provide a method for enhancing the strength and plasticity of a Zr-based amorphous alloy and a Zr-based amorphous alloy. The Zr-based amorphous alloy has both high fracture strength and plasticity.

[0004] To achieve this object, the present invention adopts the following technical solutions:

[0005] In a first aspect, the present invention provides a method for enhancing the strength and plasticity of a Zr-based amorphous alloy, comprising the following steps:

[0006] heat treating the Zr-based amorphous alloy;

[0007] The temperature of the heat treatment is 0.6 to 0.8 times the glass transition temperature of the Zr-based amorphous alloy;

[0008] Preferably, the heat treatment holding time is 5 to 20 min.

[0009] Preferably, the Zr-based amorphous alloy is Zr 45 Cu 45 Ag 10 .

[0010] Preferably, the temperature of the heat treatment is 413~553 K.

[0011] Preferably, the heating rate of the heat treatment is 5-10 k / min.

[0012] Preferably, the heat treatment holding time is 8 to 10 min.

[0013] Preferably, the heat treatment is performed in an oxygen-free environment.

[0014] Preferably, after the heat treatment is completed, the mixture is naturally cooled to room temperature.

[0015] Preferably, the Zr-based amorphous alloy is prepared according to the following method:

[0016] S1: at vacuum degree 1.5×10 -3 Pa, the weighed metal single elements are subjected to non-consumable vacuum arc melting to melt each metal single element into a master alloy ingot;

[0017] S2: The master alloy ingot is prepared into an amorphous alloy by a water-cooled copper mold suction casting method.

[0018] Preferably, the purity of the metal element is not less than 99.99%.

[0019] Preferably, the smelting is performed 6 to 8 times in step S1.

[0020] Before smelting into the master alloy ingot, the titanium ingot is pre-smelted 2 to 3 times.

[0021] Preferably, the amorphous alloy is a cylindrical block amorphous alloy, and the bottom diameter thereof is 1.5-3 mm.

[0022] Preferably, the aspect ratio of the cylindrical bulk amorphous alloy is 2:1.

[0023] In a second aspect, the present invention provides a Zr-based amorphous alloy prepared by the above method, wherein the plastic strain of the Zr-based amorphous alloy is 1.12~9.36%, and the fracture strength is 1.92~2.29 GPa.

[0024] Preferably, after heat treatment, the Zr-based amorphous alloy has a plastic strain growth rate of 1020-9260%, and a fracture strength growth rate of 12.5-25.2%.

[0025] The growth rate of the plastic strain=(plastic strain of the Zr-based amorphous alloy after heat treatment-plastic strain of the Zr-based amorphous alloy before heat treatment) / plastic strain of the Zr-based amorphous alloy before heat treatment.

[0026] The growth rate of the fracture strength=(fracture strength of the Zr-based amorphous alloy after heat treatment-fracture strength of the Zr-based amorphous alloy before heat treatment) / fracture strength of the Zr-based amorphous alloy before heat treatment.

[0027] The present invention provides a method for realizing the synergistic enhancement of the strength and plasticity of Zr-based amorphous alloys by a heat treatment process, wherein the method heat treats the Zr-based amorphous alloy, and controls the heat treatment temperature to 0.6 to 0.8 times the glass transition temperature of the amorphous alloy, and the heat treatment time is controlled to 5 to 20 min. The method provided by the present invention can cause the structural optimization of the atomic scale of the Zr-based amorphous alloy, suppress the concentration of stress during deformation, promote the nucleation, propagation and interaction of the shear band, so that the plasticity and fracture strength of the Zr-based amorphous alloy are improved, and the plasticity of the Zr-based amorphous alloy after heat treatment can reach 9.36%, and the fracture strength can reach 2289 MPa, which is compared with the Zr-based amorphous alloy that has not been heat treated. Both plasticity and fracture strength can be improved. Therefore, the method provided by the present invention helps to solve the problem of limited application of Zr-based amorphous alloys due to brittleness, and is expected to expand the application prospects of amorphous alloys.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] The present invention optimizes the microstructure of the amorphous alloy by heat treating the Zr-based amorphous alloy without changing the composition and size of the Zr-based amorphous alloy itself, thereby significantly improving the plasticity and fracture strength of the Zr-based amorphous alloy, promoting the widespread application of the amorphous alloy in industry, and being suitable for industrial production and promotion.

[0030] After testing, the plastic strain growth rate of the Zr-based amorphous alloy after heat treatment is 1020~9260%, and the fracture strength growth rate is 12.5~25.2%. It can be seen that the plastic strain and fracture strength of the Zr-based amorphous alloy provided by the present invention are significantly increased after heat treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The Zr prepared in Example 2 of the present invention 45 Cu 45 Ag 10 Amorphous alloy and Zr prepared in Comparative Example 1 45 Cu 45 Ag 10 X-ray diffraction pattern of amorphous alloy;

[0032] Figure 2 The Zr prepared in Example 2 of the present invention 45 Cu 45 Ag 10 Amorphous alloy and Zr prepared in Comparative Example 1 45 Cu 45 Ag 10 DSC curve of amorphous alloy at a heating rate of 20 K / min;

[0033] Figure 3 The Zr prepared in Example 2 of the present invention 45 Cu 45 Ag 10 Amorphous alloy and Zr prepared in Comparative Example 1 45 Cu 45 Ag 10 Engineering stress-strain curve of amorphous alloy;

[0034] Figure 4 The Zr prepared in Example 2 of the present invention 45 Cu 45 Ag 10 The fracture side morphology of amorphous alloy;

[0035] Figure 5 The Zr prepared in Example 2 of the present invention 45 Cu 45 Ag 10 Fracture surface morphology of amorphous alloy. DETAILED DESCRIPTION

[0036] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0037] In view of the problem that the plastic deformation ability of amorphous alloys is limited in the prior art, the present invention provides a method for enhancing the strength and plasticity of Zr-based amorphous alloys, comprising the following steps:

[0038] The Zr-based amorphous alloy is heat treated to obtain the alloy.

[0039] It should be noted that amorphous alloys are metastable materials, and their structure and properties are greatly affected by their composition and preparation process. Only specific compositions and suitable processes can form amorphous alloys.

[0040] In the present invention, the Zr-based amorphous alloy is preferably Zr 45 Cu 45 Ag 10 .

[0041] In the present invention, the heat treatment can optimize the microstructure of the Zr-based amorphous alloy, thereby significantly improving the plasticity and fracture strength of the Zr-based amorphous alloy.

[0042] The present invention is optimized, and it is preferred that the temperature of the heat treatment is 0.6 to 0.8 times the glass transition temperature of the Zr-based amorphous alloy, preferably 0.71 to 0.78 times. If the temperature of the heat treatment is not within this range, it is too low to effectively cause structural changes at the atomic scale inside the Zr-based amorphous alloy, and too high will lead to large-scale crystallization of the Zr-based amorphous alloy, resulting in deterioration of mechanical properties. Specifically, the temperature of the heat treatment is 413 to 553 K, which can be 413 K, 423 K, 433 K, 443 K, 453 K, 463 K, 473 K, 483 K, 493 K, 503 K, 513 K, 523 K, 533 K, 543 K or 553 K, etc., preferably 513 K.

[0043] In the present invention, the glass transition temperature is measured by a differential scanning calorimeter, and the differential scanning calorimeter model is preferably Perkin-Elmer DSC-8000.

[0044] In the present invention, the holding time of the heat treatment is 5 to 20 min, such as 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min, 19 min or 20 min, etc., preferably 8 to 10 min.

[0045] It should be noted that the holding time has an impact on the microstructure of the amorphous alloy after heat treatment. If the holding time is less than 5 min, it cannot effectively cause the structural changes of the atomic scale of the Zr-based amorphous alloy. If it is greater than 20 min, it will lead to large-scale crystallization of the Zr-based amorphous alloy, resulting in the deterioration of its mechanical properties. Therefore, the preferred holding time of the present invention is 5 to 20 min.

[0046] In the present invention, the heat treatment needs to be heated to the above temperature range at a certain heating rate. If the heating rate is too low, it will lead to large-scale crystallization of the Zr-based amorphous alloy, resulting in deterioration of its mechanical properties. If it is too high, it will not effectively cause structural changes at the atomic scale of the Zr-based amorphous alloy. Therefore, the heating rate in the present invention is preferably 5 to 10 k / min, such as 5 k / min, 6 k / min, 7 k / min, 8 k / min, 9 k / min or 10 k / min, etc.

[0047] In some embodiments of the present invention, the heat treatment is performed in an oxygen-free tube furnace. Specifically, the present invention can ensure an oxygen-free environment by introducing an inert gas into the tube furnace. The inert gas can be a gas well known to those skilled in the art, such as argon, and high-purity argon is preferred in the present invention.

[0048] In some specific embodiments of the present invention, the flow rate of the inert gas introduced into the tube furnace is 80-150 mL min -1 , preferably 80~120 mL·min -1 ; The passage time is 5 to 20 min, preferably 10 to 15 min.

[0049] In some preferred embodiments of the present invention, after the heat treatment is completed, the process is naturally cooled to room temperature. The cooling rate of the natural cooling is generally less than 10 K / min. The present invention selects natural cooling because rapid cooling will freeze the structural features at the atomic scale and cannot effectively regulate the atomic scale structure of the Zr-based amorphous alloy.

[0050] In some preferred embodiments of the present invention, the method for enhancing the strength and plasticity of a Zr-based amorphous alloy comprises the following steps:

[0051] Step 1: preparing a master alloy ingot by melting in a non-consumable vacuum arc melting furnace, and preparing a Zr-based amorphous alloy by a water-cooled copper mold suction casting method;

[0052] Step 2: Optimize the atomic-scale structure of Zr-based amorphous alloys through heat treatment.

[0053] As a further improvement of the above solution, the step 1 includes the following steps:

[0054] (1) Weighing corresponding single element raw materials according to the atomic composition of the amorphous alloy;

[0055] (2) The weighed single element is placed in a non-consumable vacuum arc melting furnace, and the chamber vacuum is pumped to 1.5×10 -3 Pa, and then filled with inert gas at -0.5 atmosphere pressure; the process parameters are: before melting the master alloy ingot, first melt the titanium ingot pre-placed in the cavity for 2 to 3 times to ensure that the cavity is an oxygen-free environment; then melt each metal element into the master alloy ingot, and the melting process is repeated 6 to 8 times;

[0056] (3) placing the master alloy ingot in a suction casting station, melting it to a molten state and then suction casting it into a copper mold, and obtaining a cylindrical block of amorphous alloy after cooling;

[0057] (4) Using a diamond wire cutting machine, the cylindrical block of amorphous alloy is cut into lengths with an aspect ratio of 2:1 as samples for subsequent heat treatment processes.

[0058] In the present invention, the purity of the metal element is not less than 99.99%; the bottom diameter of the cylindrical block of amorphous alloy is 1.5~3 mm to ensure that the amorphous alloy required by the present invention can be obtained, such as 1.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm, 2.0 mm, 2.1 mm, 2.2 mm, 2.3 mm, 2.4 mm, 2.5 mm, 2.6 mm, 2.7 mm, 2.8 mm, 2.9 mm or 3.0 mm, etc., preferably 2 mm.

[0059] As a further improvement of the above solution, the step 2 includes the following steps:

[0060] (1) The Zr-based amorphous alloy is placed in a tubular furnace and an inert protective gas, argon, is introduced to keep the Zr-based amorphous alloy in an oxygen-free environment during the heat treatment process.

[0061] (2) The sample was heated to 0.6 to 0.8 times the glass transition temperature at a heating rate of 5 K / min, kept at the highest temperature for 10 min, and then naturally cooled to room temperature.

[0062] In summary, in some embodiments of the present invention, a heat treatment process is used to achieve Zr-based amorphous alloy (Zr 45 Cu 45 Ag 10 ) A method for synergistically enhancing strength and plasticity, comprising the following steps:

[0063] (1) Weigh the corresponding single element raw materials according to the atomic composition of the amorphous alloy;

[0064] (2) Place the weighed single element in a non-consumable vacuum arc melting furnace and use a mechanical pump and a molecular pump to draw the vacuum of the chamber to 1.5×10 -3 Pa, and then filled with inert gas at -0.5 atmospheres; before melting the master alloy ingot, first melt the titanium ingot pre-placed in the cavity 2 to 3 times; then melt each metal element into a master alloy ingot, and repeat the melting process 6 to 8 times; place the master alloy ingot in the suction casting station, melt it to a molten state and then suck it into a copper mold, and after cooling, obtain a cylindrical block amorphous alloy. Use a diamond wire cutting machine to cut the cylindrical block amorphous alloy into a length with an aspect ratio of 2:1 as a sample for the subsequent heat treatment process;

[0065] (3) Place the sample in a tube furnace and introduce inert protective gas to keep the sample in an oxygen-free environment during the heat treatment. Heat the sample at a heating rate of 5 K / min to 0.6 to 0.8 times the glass transition temperature, preferably 0.71 to 0.78 times the glass transition temperature. The glass transition temperature of Zr-based amorphous alloy is 688 K, and the heat treatment temperature is more preferably 413 to 553 K. Keep at the highest temperature for 5 to 20 min, and then cool naturally to room temperature.

[0066] In the present invention, the mechanical test of the prepared Zr-based amorphous alloy adopts a microcomputer-controlled electronic universal testing machine RG / M-4300.

[0067] The Zr-based amorphous alloy (Zr 45 Cu 45 Ag 10 ), after testing, under compression at a compression rate of 0.036 mm / min, the plastic strain of the Zr-based amorphous alloy is 1.12~9.36%, and the fracture strength is 1.92~2.29 GPa; the growth rate of plastic strain is 1020~9260%, and the growth rate of fracture strength is 12.5~25.2%.

[0068] In order to further illustrate the present invention, the following examples are provided for detailed description. The experimental raw materials used in the following examples of the present invention are all common commercially available products.

[0069] Example 1

[0070] This embodiment provides a Zr-based amorphous alloy (the atomic percentage of the composition is Zr 45 Cu 45 Ag 10 ), which is achieved through a heat treatment process and specifically comprises the following steps:

[0071] (1) Take metal elements zirconium, copper and silver with a purity greater than 99.99%, and weigh the corresponding metal elements according to their atomic composition;

[0072] (2) Place the weighed single element in a non-consumable vacuum arc melting furnace and use a mechanical pump and a molecular pump to draw the vacuum of the chamber to 1.5×10 -3Pa, and then filled with high-purity argon gas at -0.5 atmospheres; before melting the master alloy ingot, first melt the titanium ingot pre-placed in the cavity 3 times, each melting time is 30 s; then melt each metal element into the master alloy ingot, the melting process is 8 times, each melting time is 30 s; place the master alloy ingot in the suction casting station, melt it to a molten state, and then suck it into a copper mold, and after cooling, a cylindrical block amorphous alloy with a diameter of 2 mm is obtained. Use a diamond wire cutting machine to cut the cylindrical block amorphous alloy into a length with an aspect ratio of 2:1 as a sample for the subsequent heat treatment process;

[0073] (3) Place the sample in a tube furnace and introduce high-purity argon gas to keep the sample in an oxygen-free environment during the heat treatment process. Heate the sample to 493 K at a heating rate of 5 K / min, keep it at the highest temperature for 10 min, and then cool it naturally to room temperature.

[0074] The cylindrical Zr with a length of 4 mm and a diameter of 2 mm prepared in this embodiment 45 Cu 45 Ag 10 Bulk amorphous alloy and as-cast Zr without heat treatment 45 Cu 45 Ag 10 The compression test data of the amorphous alloy at a compression rate of 0.036 mm / min are shown in Table 1.

[0075] Table 1

[0076]

[0077] Example 2

[0078] This embodiment provides a Zr-based amorphous alloy (the atomic percentage of the composition is Zr 45 Cu 45 Ag 10 ), which is achieved through a heat treatment process and specifically comprises the following steps:

[0079] (1) Take metal elements zirconium, copper and silver with a purity greater than 99.99% and weigh the corresponding metal elements according to their atomic composition.

[0080] (2) Place the weighed single element in a non-consumable vacuum arc melting furnace and use a mechanical pump and a molecular pump to draw the vacuum of the chamber to 1.5×10 -3Pa, and then filled with high-purity argon gas at -0.5 atmospheres; before melting the master alloy ingot, first melt the titanium ingot pre-placed in the cavity three times, each melting time is 30 s; then melt each metal element into the master alloy ingot, the melting process is 8 times, each melting time is 30 s; the master alloy ingot is placed in the suction casting station, melted to a molten state, and then sucked into a copper mold, and cooled to obtain a cylindrical bulk amorphous alloy with a diameter of 2 mm. The cylindrical bulk amorphous alloy is cut into a length with an aspect ratio of 2:1 using a diamond wire cutting machine as a sample for the subsequent heat treatment process.

[0081] (3) Place the sample in a tube furnace and introduce high-purity argon gas to keep the sample in an oxygen-free environment during the heat treatment process. Heating the sample to 513 K at a heating rate of 5 K / min, keeping it at the highest temperature for 10 min, and then cooling it naturally to room temperature.

[0082] The cylindrical Zr with a length of 4 mm and a diameter of 2 mm prepared in this embodiment 45 Cu 45 Ag 10 Bulk amorphous alloy and as-cast Zr without heat treatment 45 Cu 45 Ag 10 The compression test data of the amorphous alloy at a compression rate of 0.036 mm / min are shown in Table 2.

[0083] Table 2

[0084]

[0085] Example 3

[0086] This embodiment provides a Zr-based amorphous alloy (the atomic percentage of the composition is Zr 45 Cu 45 Ag 10 ), which is achieved through a heat treatment process and specifically comprises the following steps:

[0087] (1) Take metal elements zirconium, copper and silver with a purity greater than 99.99% and weigh the corresponding metal elements according to their atomic composition.

[0088] (2) Place the weighed single element in a non-consumable vacuum arc melting furnace and use a mechanical pump and a molecular pump to draw the vacuum of the chamber to 1.5×10 -3Pa, and then filled with high-purity argon gas at -0.5 atmospheres; before melting the master alloy ingot, first melt the titanium ingot pre-placed in the cavity three times, each melting time is 30 s; then melt each metal element into the master alloy ingot, the melting process is 8 times, each melting time is 30 s; the master alloy ingot is placed in the suction casting station, melted to a molten state, and then sucked into a copper mold, and cooled to obtain a cylindrical bulk amorphous alloy with a diameter of 2 mm. The cylindrical bulk amorphous alloy is cut into a length with an aspect ratio of 2:1 using a diamond wire cutting machine as a sample for the subsequent heat treatment process.

[0089] (3) Place the sample in a tube furnace and introduce high-purity argon gas to keep the sample in an oxygen-free environment during the heat treatment process. Heate the sample to 533 K at a heating rate of 5 K / min, keep it at the highest temperature for 10 min, and then cool it naturally to room temperature.

[0090] The cylindrical Zr with a length of 4 mm and a diameter of 2 mm prepared in this embodiment 45 Cu 45 Ag 10 Bulk amorphous alloy and as-cast Zr without heat treatment 45 Cu 45 Ag 10 The compression test data of the amorphous alloy at a compression rate of 0.036 mm / min are shown in Table 3.

[0091] Table 3

[0092]

[0093] Example 4

[0094] This embodiment provides a Zr-based amorphous alloy (the atomic percentage of the composition is Zr 45 Cu 45 Al 10 ), which is achieved through a heat treatment process and specifically comprises the following steps:

[0095] (1) Take metal elements zirconium, copper and aluminum with a purity greater than 99.99%, and weigh the corresponding metal elements according to their atomic composition;

[0096] (2) Place the weighed single element in a non-consumable vacuum arc melting furnace and use a mechanical pump and a molecular pump to draw the vacuum of the chamber to 1.5×10 -3Pa, and then filled with high-purity argon gas at -0.5 atmospheres; before melting the master alloy ingot, first melt the titanium ingot pre-placed in the cavity 3 times, each melting time is 30 s; then melt each metal element into the master alloy ingot, the melting process is 8 times, each melting time is 30 s; place the master alloy ingot in the suction casting station, melt it to a molten state, and then suck it into a copper mold, and after cooling, a cylindrical block amorphous alloy with a diameter of 2 mm is obtained. Use a diamond wire cutting machine to cut the cylindrical block amorphous alloy into a length with an aspect ratio of 2:1 as a sample for the subsequent heat treatment process;

[0097] (3) Place the sample in a tube furnace and introduce high-purity argon gas to keep the sample in an oxygen-free environment during the heat treatment process. Heate the sample to 493 K at a heating rate of 5 K / min, keep it at the highest temperature for 10 min, and then cool it naturally to room temperature.

[0098] The cylindrical Zr with a length of 4 mm and a diameter of 2 mm prepared in this embodiment 45 Cu 45 Al 10 Bulk amorphous alloy and as-cast Zr without heat treatment 45 Cu 45 Al 10 The compression test data of the amorphous alloy at a compression rate of 0.036 mm / min are shown in Table 4.

[0099] Table 4

[0100]

[0101] Comparative Example 1

[0102] This comparative example provides a Zr-based amorphous alloy (the atomic percentage of the composition is Zr 45 Cu 45 Ag 10 ), compared with the example, the difference is that this comparative example does not undergo heat treatment, and specifically comprises the following steps:

[0103] (1) Take metal elements zirconium, copper and silver with a purity greater than 99.99% and weigh the corresponding metal elements according to their atomic composition.

[0104] (2) Place the weighed single element in a non-consumable vacuum arc melting furnace and use a mechanical pump and a molecular pump to draw the vacuum of the chamber to 1.5×10 -3Pa, and then filled with high-purity argon gas at -0.5 atmospheres; before melting the master alloy ingot, first melt the titanium ingot pre-placed in the cavity three times, each melting time is 30 s; then melt each metal element into the master alloy ingot, the melting process is 8 times, each melting time is 30 s; the master alloy ingot is placed in the suction casting station, melted to a molten state, and then sucked into a copper mold, and cooled to obtain a cylindrical bulk amorphous alloy with a diameter of 2 mm. The cylindrical bulk amorphous alloy is cut into a length with an aspect ratio of 2:1 using a diamond wire cutting machine.

[0105] The cylindrical bulk amorphous alloy Cu45Zr prepared in this comparative example has a length of 4 mm and a diameter of 2 mm. 45 Ag 10 The compression test data at a compression rate of 0.036 mm / min are shown in Table 5.

[0106] Table 5

[0107]

[0108] In the present invention, the Zr prepared in Example 2 45 Cu 45 Ag 10 Amorphous alloy and Zr prepared in Comparative Example 1 45 Cu 45 Ag 10 The X-ray diffraction diagram, DSC curve and stress-strain curve of the amorphous alloy at a heating rate of 20 K / min are shown in Figure 2. Figures 1 to 3 As shown. Figure 1 It can be seen that after heat treatment, the sample as a whole is still an amorphous structure; Figure 2 It can be seen that the sample still exhibits glass transition behavior and is still an amorphous structure. Figure 3 It can be seen that after heat treatment, the strength and plasticity of Zr-based amorphous alloys are improved, achieving synergistic enhancement of strength and plasticity.

[0109] Example 2: Zr 45 Cu 45 Ag 10 The fracture side morphology and fracture surface morphology of amorphous alloy are shown in Figure 2. Figure 4 and Figure 5 As shown. Figure 4 and Figure 5 It can be seen that the shear bands on the side of the specimen are dense and intertwined, which effectively reduces stress concentration and improves the plastic deformation capacity of the specimen. The fracture surface of the specimen presents a dense and uniform vein distribution, which also proves the excellent plastic deformation capacity of the specimen.

[0110] Comparative Example 2

[0111] This comparative example provides a Zr-based amorphous alloy (the atomic percentage of the composition is Zr 45 Cu 45 Ag 10 ), compared with the embodiment, the difference is that the heat treatment temperature in this comparative example is from the glass transition temperature to the crystallization temperature, and specifically comprises the following steps:

[0112] (1) Take metal elements zirconium, copper and silver with a purity greater than 99.99% and weigh the corresponding metal elements according to their atomic composition.

[0113] (2) Place the weighed single element in a non-consumable vacuum arc melting furnace and use a mechanical pump and a molecular pump to draw the vacuum of the chamber to 1.5×10 -3 Pa, and then filled with high-purity argon gas at -0.5 atmospheres; before melting the master alloy ingot, first melt the titanium ingot pre-placed in the cavity three times, each melting time is 30 s; then melt each metal element into the master alloy ingot, the melting process is 8 times, each melting time is 30 s; the master alloy ingot is placed in the suction casting station, melted to a molten state, and then sucked into a copper mold, and cooled to obtain a cylindrical bulk amorphous alloy with a diameter of 2 mm. The cylindrical bulk amorphous alloy is cut into a length with an aspect ratio of 2:1 using a diamond wire cutting machine.

[0114] (3) Place the sample in a tube furnace and introduce high-purity argon gas to keep the sample in an oxygen-free environment during the heat treatment process. Heate the sample to 698 K at a heating rate of 5 K / min, keep it at the highest temperature for 10 min, and then cool it naturally to room temperature.

[0115] The cylindrical bulk amorphous alloy Cu45Zr prepared in this comparative example has a length of 4 mm and a diameter of 2 mm. 45 Ag 10 The compression test data at a compression rate of 0.036 mm / min are shown in Table 6.

[0116] Table 6

[0117]

[0118] It can be seen from the above embodiments and comparative examples that the present invention provides a method for realizing the synergistic enhancement of strength and plasticity of Zr-based amorphous alloy by heat treatment process, wherein the atomic percentage of the Zr-based bulk amorphous alloy is Zr 45 Cu 45 Ag 10Through heat treatment process, the atomic structure of amorphous alloy is optimized, the plasticity and fracture strength of the material are significantly improved, and the overall mechanical properties of the material are enhanced. The compression test results show that the fracture strength of the heat-treated bulk amorphous alloy is 1.92~2.29 GPa and the plastic strain is 1.12~9.36% under compression rate of 0.036 mm / min.

[0119] In summary, the heat treatment method provided by the present invention is low-cost, simple and efficient, optimizes the microstructure of the amorphous alloy, and significantly improves the plasticity and fracture strength of the Zr-based amorphous alloy.

[0120] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for enhancing the strength and plasticity of a Zr-based amorphous alloy, characterized in that: The following steps are involved: heat treating the Zr-based amorphous alloy; The temperature of the heat treatment is 0.6 to 0.8 times the glass transition temperature of the Zr-based amorphous alloy; The heat treatment holding time is 5 to 20 min.

2. The method according to claim 1, characterized in that The Zr-based amorphous alloy is Zr 45 Cu 45 Ag 10 .

3. The method according to claim 1 or 2, characterized in that: The temperature of the heat treatment is 413~553 K; The heating rate of the heat treatment is 5-10 k / min; The heat treatment holding time is 8 to 10 min.

4. The method according to any one of claims 1 to 3, characterized in that The heat treatment is performed in an oxygen-free environment.

5. The method according to any one of claims 1 to 4, characterized in that After the heat treatment is completed, the mixture is naturally cooled to room temperature.

6. The method according to any one of claims 1 to 5, characterized in that The Zr-based amorphous alloy is prepared according to the following method: S1: at vacuum degree 1.5×10 -3 Pa, the weighed metal single elements are subjected to non-consumable vacuum arc melting to melt each metal single element into a master alloy ingot; S2: The master alloy ingot is prepared into an amorphous alloy by a water-cooled copper mold suction casting method.

7. The method according to claim 6, characterized in that The purity of the metal element is not less than 99.99%.

8. The method according to claim 6 or 7, characterized in that: The number of smelting in step S1 is 6 to 8 times; Before smelting into the master alloy ingot, the titanium ingot is pre-smelted 2 to 3 times.

9. The method according to any one of claims 6 to 8, characterized in that The amorphous alloy is a cylindrical block amorphous alloy, and the bottom diameter thereof is 1.5-3 mm.

10. The Zr-based amorphous alloy prepared by the method according to any one of claims 1 to 9, characterized in that: The plastic strain of the Zr-based amorphous alloy is 1.12-9.36%, and the fracture strength is 1.92-2.29 GPa; After the Zr-based amorphous alloy is heat treated, the growth rate of plastic strain is 1020-9260%, and the growth rate of fracture strength is 12.5-25.2%.

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