A Zr-Ti-Ni-V-based amorphous alloy and an amorphous / nanocrystalline composite alloy and a preparation method thereof

Abstract

The present invention belongs to the field of amorphous alloy materials, and particularly relates to a novel Zr-Ti-Ni-V-based amorphous alloy and an amorphous / nanocrystalline composite alloy. The chemical composition expression of this series of alloys is: Zr a Ti b Ni c V d , where a, b, c, and d respectively represent the atomic percentages of the corresponding components Zr, Ti, Ni, and V. Among them, 37 ≤ a ≤ 65, 15 ≤ b ≤ 55, 15 ≤ c ≤ 40, 2 ≤ d ≤ 6, and a + b + c + d = 100. This series of alloys has a high amorphous formation ability, and can be prepared into continuous flexible alloy ribbons with an amorphous structure or an amorphous / nanocrystalline composite structure by the melt spinning quenching method, and at the same time has a low liquidus temperature. The Zr-Ti-Ni-V-based amorphous alloy and the amorphous / nanocrystalline composite alloy developed by the present invention can be used as a kind of brazing material.

Description

Technical Field

[0001] The present invention belongs to the field of amorphous alloy materials, and particularly relates to a Zr-Ti-Ni-V-based amorphous alloy and an amorphous / nanocrystalline composite alloy with high amorphous formation ability and low liquidus temperature. Background Art

[0002] Amorphous alloy materials prepared by rapid solidification methods exhibit a series of unique physical, chemical, and mechanical properties due to their structural characteristics of long-range disorder and short-range order in the internal atomic arrangement, such as high strength, high elasticity, and high corrosion resistance. Therefore, the composition design, properties, and practical applications of amorphous alloy materials have become one of the important research directions in the field of materials.

[0003] As one of the important amorphous alloy composition systems, zirconium-based amorphous alloys have been widely studied. Currently, a series of zirconium-based amorphous alloy composition systems with high amorphous formation ability have been developed, such as Zr-Al-Ni-Cu, Zr-Ti-Cu-Ni-Be, Zr-Al-Co-Ag, Zr-Al-Fe(-Cu), etc. These alloys exhibit high strength, high elasticity, high hardness, and good corrosion resistance. Brazing materials are one of the important application directions of Zr-based amorphous alloys, and have the advantages of being easily prepared into continuous ductile thin strips for convenient use as brazing materials, uniform composition, pure material, and narrow melting temperature range. Currently, the existing Zr-based amorphous alloys contain highly toxic elements such as Be or noble metal elements, or contain relatively high contents of elements such as Cu, Co, and Fe, and are prone to form brittle intermetallic compounds with elements such as Ti in the base material during the brazing process, thereby reducing the mechanical properties of the joint and being unfavorable for their practical applications. Therefore, developing new Zr-based amorphous alloys without highly toxic elements, low cost, and suitable for use as brazing materials has important application value. Summary of the Invention

[0004] To solve the above problems, the present invention provides a new Zr-Ti-Ni-V-based amorphous alloy and an amorphous / nanocrystalline composite alloy. The chemical composition expression of the alloy is: Zr a Ti b Ni c V d , where a, b, c, and d respectively represent the atomic percentages of the corresponding components Zr, Ti, Ni, and V, and 37 ≤ a ≤ 65, 15 ≤ b ≤ 55, 15 ≤ c ≤ 40, 2 ≤ d ≤ 6, and a + b + c + d = 100. This alloy has a simple composition, few components, and does not contain noble metal elements and toxic elements.

[0005] Preferably, it is prepared into an alloy thin strip with a thickness of 10 - 80 μm and having an amorphous structure or an amorphous / nanocrystalline composite structure by the melt spinning method.

[0006] Preferably, the phase composition of the alloy is related to both the alloy composition and the thickness of the alloy ribbon. When the chemical composition of the alloy is 37 ≤ a ≤ 65, 15 ≤ b ≤ 25, 20 < c ≤ 40, 2 ≤ d ≤ 6, the alloy ribbon with a thickness of 10 - 80 μm has an amorphous structure; when the chemical composition of the alloy is 37 ≤ a ≤ 50, 25 < b ≤ 40, 15 ≤ c ≤ 30, 2 ≤ d ≤ 6, the alloy ribbon with 10 ≤ thickness < 40 μm has an amorphous structure, and the alloy ribbon with a thickness of 40 - 80 μm has an amorphous / nanocrystalline duplex structure; when the chemical composition of the alloy is 50 < a ≤ 65, 20 ≤ b ≤ 55, 15 ≤ c ≤ 20, 2 ≤ d ≤ 6 or 40 ≤ a ≤ 45, 40 < b ≤ 55, 15 ≤ c ≤ 20, 2 ≤ d ≤ 6, the alloy ribbon with 10 ≤ thickness < 20 μm has an amorphous structure, and the alloy ribbon with a thickness of 20 - 80 μm has an amorphous / nanocrystalline duplex structure.

[0007] Preferably, the size of the nanocrystals in the amorphous / nanocrystalline composite structure is 5 - 100 nm.

[0008] Preferably, the liquidus temperature of the alloy is 900 K - 1400 K.

[0009] The Zr-Ti-Ni-V series alloy of the present invention has good amorphous formation ability, and can be prepared by the melt spinning method to obtain a continuous and flexible alloy ribbon with a thickness of 10 - 80 μm having an amorphous structure or an amorphous / nanocrystalline duplex structure. Its surface quality is good, the edges are flat, and it has a relatively low liquidus temperature, and can be used as a type of brazing material.

[0010] The present invention also provides a method for preparing a novel Zr-Ti-Ni-V series amorphous alloy and an amorphous / nanocrystalline duplex alloy, and the specific preparation steps are as follows:

[0011] Step 1: Convert the characteristic components of the alloy from atomic percentages to mass percentages, and weigh the elemental metal raw materials of each component with a balance for alloy batching;

[0012] Step 2: Put the raw materials proportioned in Step 1 into a vacuum arc melting furnace, evacuate to make the vacuum degree in the furnace reach 3×10 -3 ~5×10 -3 Pa, and then fill with argon as a protective gas; adjust the arc current to 100 - 150 A, and remelt the alloy ingot 3 - 5 times to ensure uniform composition. After the alloy ingot cools to room temperature with the furnace, take it out to obtain a master alloy ingot;

[0013] Step 3: Mechanically crush the master alloy ingot into small pieces, take about 3 - 5 g from them and place it in a quartz tube with an opening at the bottom. Put the quartz tube and the alloy raw materials as a whole into the melt spinning quenching equipment, and adjust the distance between the opening at the bottom of the quartz tube and the surface of the copper wheel to about 1 - 2 mm; evacuate to make the vacuum degree in the cavity of the melt spinning quenching equipment reach 2×10 -2 Pa, and then fill it with argon as the protective gas; set the rotation speed of the copper wheel to 10 - 60 m / s, the spraying pressure to 0.02 - 0.05 MPa, and the induction heating current to 5 - 10 A; use the induction heating method to melt the master alloy, and then use argon to spray the molten alloy from the opening at the bottom of the quartz tube onto the high-speed rotating copper wheel, so as to obtain the novel Zr-Ti-Ni-V series amorphous alloy and amorphous / nanocrystalline composite alloy thin strips.

[0014] Advantages of the present invention compared with the prior art:

[0015] A novel Zr-Ti-Ni-V series amorphous alloy and amorphous / nanocrystalline composite alloy disclosed by the present invention has a relatively high total content of Zr and Ti and a relatively low Ni content. This series of alloys does not contain toxic elements and precious metal elements, has a simple composition, is convenient for smelting, and can be net-shaped into continuous and flexible alloy thin strips with an amorphous structure or an amorphous / nanocrystalline composite structure by the method of rapid solidification. It has a relatively low liquidus temperature and can be used as a kind of brazing material for the brazing connection of materials such as titanium alloys, titanium aluminide intermetallic compounds, superalloys, and ceramics, further expanding the composition system and practical application range of amorphous alloys and amorphous / nanocrystalline composite alloys. Description of the Drawings

[0016] Figure 1 Macrophotograph of the Zr 47 Ti 17 Ni 33 V3 alloy thin strip in Example 1 of the present invention.

[0017] Figure 2 XRD pattern of the Zr 47 Ti 17 Ni 33 V3 amorphous alloy in Example 1 of the present invention.

[0018] Figure 3 DSC curve of the Zr 47 Ti 17 Ni 33 V3 amorphous alloy in Example 1 of the present invention.

[0019] Figure 4 Macrophotograph of the Zr 47 Ti 29 Ni 21 V3 alloy thin strip in Example 2 of the present invention.

[0020] Figure 5 For Zr in Embodiment 2 of the present invention 47 Ti 29 Ni 21 XRD patterns of V3 amorphous alloy and amorphous / nanocrystalline composite alloy

[0021] Figure 6 For Zr in Embodiment 2 of the present invention 47 Ti 29 Ni 21 DSC curve of V3 amorphous alloy

[0022] Figure 7 For Zr in Embodiment 3 of the present invention 59 Ti 23 Ni 15 Macroscopic photograph of V3 alloy ribbon

[0023] Figure 8 For Zr in Embodiment 3 of the present invention 59 Ti 23 Ni 15 XRD pattern of V3 amorphous / nanocrystalline composite alloy

[0024] Figure 9 For Zr in Embodiment 3 of the present invention 59 Ti 23 Ni 15 DSC curve of V3 amorphous / nanocrystalline composite alloy

[0025] Figure 10 XRD patterns of Zr-Ti-Ni-V series amorphous alloy and amorphous / nanocrystalline composite alloy in Table 1

[0026] Figure 11 (a)-11(b) and Figure 12 (a)-12(b) are DSC curves of Zr-Ti-Ni-V series amorphous alloy and amorphous / nanocrystalline composite alloy in Table 1

[0027] Figure 13 For TC4 / Zr in Embodiment 4 of the present invention 41 Ti 29 Ni 27 Backscattered electron image of V3 / TC4 joint

[0028] Figure 14 For TC4 / Zr in Embodiment 5 of the present invention 41 Ti 35 Ni 21 Backscattered electron image of V3 / TC4 joint

[0029] Figure 15 For TC4 / Zr in Embodiment 6 of the present invention47 Ti 29 Ni 21 Backscattered electron image of V3 / TC4 joint. Detailed implementation mode

[0030] To further illustrate the present invention, the present invention will be described below in conjunction with embodiments, drawings, etc. It should be understood that these embodiments are implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operation processes are given. It is only to further illustrate the features and advantages of the present invention, rather than a limitation on the claims of the present invention. The protection scope of the present invention should include all the contents of the claims and is not limited to the following embodiments.

[0031] Embodiment 1

[0032] Prepare Zr of the present invention 47 Ti 17 Ni 33 V3 amorphous alloy:

[0033] Step 1: Convert the atomic ratio of each element in Zr 47 Ti 17 Ni 33 V3 into mass percentages, and weigh the elemental metal raw materials of each group with a balance for alloy batching;

[0034] Step 2: Put the raw materials proportioned in Step 1 into a vacuum arc melting furnace, evacuate to make the vacuum degree in the furnace reach 3×10 -3 ~5×10 -3 Pa, and then fill argon as a protective gas; adjust the arc current to 100 - 150 A, and remelt the alloy ingot 3 - 5 times to ensure uniform alloy composition. After the alloy ingot cools to room temperature with the furnace, take it out to obtain the master alloy ingot;

[0035] Step 3: Mechanically crush the master alloy ingot into small pieces, take about 3 - 5 grams from it and place it in a quartz tube with an open bottom. Put the quartz tube and the alloy raw materials as a whole into a melt spinning and quenching device, and adjust the distance between the open bottom of the quartz tube and the surface of the copper wheel to about 1 - 2 mm; evacuate to make the vacuum degree in the cavity of the melt spinning and quenching device reach 2×10 -2 Pa, and then fill argon as a protective gas; set the copper wheel speed to 10 - 60 m / s, the injection pressure to 0.02 - 0.05 MPa, and the induction heating current to 5 - 10 A. Use the induction heating method to melt the master alloy, and then use argon to spray the melted alloy from the open bottom of the quartz tube onto the high-speed rotating copper wheel, so as to obtain a smooth and continuous flexible Zr 47 Ti 17 Ni 33 V3 alloy thin strip ( Figure 1 ).

[0036] Step 4: Perform X-ray diffraction analysis (XRD) on the prepared Zr thin ribbons with thicknesses of 35 and 60 μm 47 Ti 17 Ni 33 V3 amorphous alloy thin ribbons respectively. Their XRD patterns ( Figure 2 ) all show relatively broad diffuse scattering peaks and no crystal diffraction peaks appear, proving that they are in amorphous structure.

[0037] Step 5: Use a differential scanning calorimeter (DSC) to perform thermal analysis ( 47 Ti 17 Ni 33 V3 amorphous alloy thin ribbons with a thickness of 35 μm prepared. Its DSC curve has obvious glass transition and crystallization exothermic peaks, further proving that it is in amorphous structure. Its glass transition temperature is 572 K, crystallization temperature is 657 K, and liquidus temperature is 1213 K. Figure 3 )

[0038] Example 2

[0039] Prepare the Zr 47 Ti 29 Ni 21 V3 amorphous alloy and amorphous / nanocrystalline composite alloy of the present invention:

[0040] Step 1: Convert the atomic ratios of the elements in Zr 47 Ti 29 Ni 21 V3 into mass percentages, and use a balance to weigh the elemental metal raw materials of each component for alloy batching;

[0041] Step 2: Put the raw materials proportioned in Step 1 into a vacuum arc melting furnace, evacuate to make the vacuum degree in the furnace reach 3×10 -3 ~5×10 -3 Pa, and then fill in argon as the protective gas; adjust the arc current to 100 - 150 A, and remelt the alloy ingot 3 - 5 times to ensure uniform alloy composition. After the alloy ingot cools to room temperature with the furnace, take it out to obtain the master alloy ingot;

[0042] Step 3: Mechanically crush the master alloy ingot into small pieces, take about 3 - 5 grams from it and place it in a quartz tube with an open bottom. Put the quartz tube and the alloy raw materials as a whole into a melt spinning quenching device, and adjust the distance between the open bottom of the quartz tube and the surface of the copper wheel to about 1 - 2 mm; evacuate to make the vacuum degree in the cavity of the melt spinning quenching device reach 2×10 -2Pa, and then argon is filled as the protective gas; the rotation speed of the copper wheel is set to be 10 - 60 m / s, the spraying pressure is 0.02 - 0.05 MPa, and the induction heating current is 5 - 10 A. The master alloy is melted by induction heating, and then the melted alloy is sprayed from the bottom opening of the quartz tube onto the high-speed rotating copper wheel by argon, so as to obtain a Zr 47 Ti 29 Ni 21 V3 alloy thin strip( Figure 4 ).

[0043] Step 4: The prepared Zr 47 Ti 29 Ni 21 V3 alloy thin strips with thicknesses of 35, 40, and 45 μm are respectively subjected to X-ray diffraction analysis (XRD). The results( Figure 5 ) show that: the XRD pattern of the alloy thin strip with a thickness of 35 μm only has a diffuse scattering peak corresponding to the amorphous phase, and no crystal diffraction peak appears, proving that it is an amorphous structure; the XRD patterns of the alloy thin strips with thicknesses of 40 μm and 45 μm have diffraction peaks corresponding to the nanocrystalline structure superimposed on the diffuse scattering peak corresponding to the amorphous structure, proving that it has an amorphous / nanocrystalline composite structure. The calculated size of the nanocrystals is about 17 nm.

[0044] Step 5: The prepared Zr 47 Ti 29 Ni 21 V3 amorphous alloy thin strip is subjected to thermal analysis( Figure 6 ). There are obvious glass transition and crystallization exothermic peaks on its DSC curve, further proving that it is an amorphous structure. Its glass transition temperature is 649 K, the crystallization temperature is 686 K, and the liquidus temperature is 1143 K.

[0045] Example 3

[0046] Prepare the Zr 59 Ti 23 Ni 15 V3 amorphous / nanocrystalline composite alloy of the present invention:

[0047] Step 1: Convert the atomic ratio of each element in Zr 59 Ti 23 Ni 15 V3 into mass percentages, and weigh the elemental metal raw materials of each component with a balance for alloy batching;

[0048] Step 2: Put the raw materials proportioned in Step 1 into a vacuum arc melting furnace, evacuate to make the vacuum degree in the furnace reach 3×10 -3 ~5×10 -3Pa, and then argon gas is filled as the protective gas; the arc current is adjusted to 100 - 150 A, and the alloy ingot is remelted 3 - 5 times to ensure uniform alloy composition. After the alloy ingot is cooled to room temperature in the furnace, it is taken out to obtain the master alloy ingot;

[0049] Step 3: Mechanically crush the master alloy ingot into small pieces, take about 3 - 5 g from them and place it in a quartz tube with an opening at the bottom. The quartz tube and the alloy raw materials are put into the melt spinning quenching equipment as a whole, and the distance between the opening at the bottom of the quartz tube and the surface of the copper wheel is adjusted to about 1 - 2 mm; evacuate to make the vacuum degree in the cavity of the melt spinning quenching equipment reach 2×10 -2 Pa, and then argon gas is filled as the protective gas; the rotation speed of the copper wheel is set to 10 - 60 m / s, the spraying pressure is 0.02 - 0.05 MPa, and the induction heating current is 5 - 10 A. The master alloy is melted by induction heating, and then the melted alloy is sprayed from the opening at the bottom of the quartz tube onto the high-speed rotating copper wheel by argon gas, so as to obtain a smooth and continuous flexible Zr 59 Ti 23 Ni 15 V3 alloy thin strip( Figure 7 ).

[0050] Step 4: Perform X-ray diffraction analysis (XRD) on the prepared Zr 59 Ti 23 Ni 15 V3 alloy thin strip with a thickness of 25 μm. Its XRD pattern( Figure 8 ) shows that there are diffraction peaks corresponding to the nanocrystalline structure superimposed on the diffuse scattering peak corresponding to the amorphous structure, proving that it has an amorphous / nanocrystalline composite structure. The size of the nanocrystals can be calculated to be about 12 nm.

[0051] Step 5: Use a differential scanning calorimeter (DSC) to perform thermal analysis( 59 Ti 23 Ni 15 ) on the prepared Zr Figure 9 V3 amorphous / nanocrystalline composite alloy thin strip. There is a crystallization exothermic peak on its DSC curve, proving that it has an amorphous / nanocrystalline composite structure. Its crystallization temperature is 590 K, and the liquidus temperature is 1124 K.

[0052] In the present invention, the Zr-Ti-Ni-V alloy compositions shown in Table 1 are prepared by the same method as in Examples 1 - 3. The prepared products are analyzed by XRD and DSC, and all have an amorphous structure or an amorphous / nanocrystalline composite structure, and have a lower liquidus temperature. The XRD patterns and DSC curves corresponding to the Zr-Ti-Ni-V alloys in Table 1 are as Figures 10 - 12 shown.

[0053] Table 1 Amorphous formation ability and liquidus temperature of Zr-Ti-Ni-V alloy

[0054]

[0055]

[0056] Example 4

[0057] Using the Zr 41 Ti 29 Ni 27 V3 amorphous alloy as filler metal to vacuum brazing aerospace titanium alloy Ti-6Al-4V (TC4):

[0058] Step 1: Grind the surface of TC4 alloy successively with 60#, 200#, 500#, and 1000# sandpapers, and then ultrasonically clean the Zr 41 Ti 29 Ni 27 V3 amorphous alloy ribbon and TC4 alloy in acetone, absolute ethanol, and distilled water in turn to remove the oil and impurities on the surface, and then take them out and dry.

[0059] Step 2: Assemble the brazing specimen in a lap joint manner. The required plate size of the lap joint specimen is 10mm×30mm×3mm, and the size of the lap joint part is 10mm×3mm. During assembly, place the Zr 41 Ti 29 Ni 27 V3 amorphous alloy ribbon between the base metals to form a sandwich structure of TC4 / Zr 41 Ti 29 Ni 27 V3 / TC4.

[0060] Step 3: Place the lap joint specimen in a vacuum brazing furnace, evacuate the furnace chamber, and when the vacuum degree is less than 5×10 -3 Pa, heat it up to 1233K (960°C) at a heating rate of 10K / min, then hold for 30min, and after welding, wait for the specimen to cool to room temperature with the furnace and then take it out.

[0061] Step 4: Use an electron probe microanalyzer (EPMA) to analyze the microstructure of the TC4 / Zr 41 Ti 29 Ni 27 V3 / TC4 joint. The backscattered electron image of the joint is as Figure 13 shown. There are no defects such as pores and cracks in the joint, and good metallurgical bonding is achieved. The brazing seam area is mainly lamellar structure.

[0062] Step 5: Use a universal testing machine to test the TC4 / Zr 41 Ti 29Ni 27 The tensile shear performance of the V3 / TC4 lap joint was tested, and its tensile shear strength was 410 MPa.

[0063] Example 5

[0064] Using Zr of the present invention 41 Ti 35 Ni 21 The V3 amorphous alloy was used as a filler metal for vacuum brazing the aerospace titanium alloy Ti-6Al-4V (TC4):

[0065] Step 1: The TC4 alloy was successively polished on the surface with 60#, 200#, 500#, and 1000# sandpapers, and then the Zr 41 Ti 35 Ni 21 V3 amorphous alloy ribbon and the TC4 alloy were ultrasonically cleaned in acetone, absolute ethanol, and distilled water in sequence to remove the oil and impurities on the surface, and then taken out and dried.

[0066] Step 2: The brazing specimens were assembled in a lap joint manner. The required plate size for the lap specimens was 10 mm × 30 mm × 3 mm, and the size of the lap part was 10 mm × 3 mm. During assembly, the Zr 41 Ti 35 Ni 21 V3 amorphous alloy ribbon was pre-placed between the base metals to form a sandwich structure of TC4 / Zr 41 Ti 35 Ni 21 V3 / TC4.

[0067] Step 3: The lap specimens were placed in a vacuum brazing furnace, and the furnace chamber was evacuated. After the vacuum degree was less than 5×10 -3 Pa, it was heated to 1233 K (960 °C) at a heating rate of 10 K / min, then held for 30 min, and after welding, the specimens were taken out after cooling to room temperature with the furnace.

[0068] Step 4: The microstructure of the TC4 / Zr 41 Ti 35 Ni 21 V3 / TC4 joint was analyzed by electron probe microanalysis (EPMA). The backscattered electron image of the joint is as Figure 14 shown. There are no defects such as pores and cracks in the joint, achieving good metallurgical bonding. The brazing seam area is mainly lamellar structure.

[0069] Step 5: The tensile shear performance of the TC4 / Zr 41 Ti 35 Ni 21 V3 / TC4 lap joint was tested, and its tensile shear strength was 330 MPa.

[0070] Example 6

[0071] Using the Zr of the present invention 47 Ti 29 Ni 21 V3 amorphous alloy as filler metal for vacuum brazing of aerospace titanium alloy Ti-6Al-4V (TC4):

[0072] Step 1: The TC4 alloy was polished successively with 60#, 200#, 500#, and 1000# sandpapers on the surface, and then the Zr 47 Ti 29 Ni 21 V3 amorphous alloy ribbon and the TC4 alloy were ultrasonically cleaned successively in acetone, absolute ethanol, and distilled water to remove oil and impurities on the surface, and then taken out and dried.

[0073] Step 2: Two methods, lap joint and butt joint, were adopted during the assembly of the brazing specimens. The required plate size for the lap joint specimens was 10 mm×30 mm×3 mm, and the size of the lap part was 10 mm×3 mm. The required plate size for the butt joint specimens was 5 mm×10 mm×27.5 mm, and the size of the butt joint surface was 5 mm×10 mm. During assembly, the Zr 47 Ti 29 Ni 21 V3 amorphous alloy ribbon was pre-placed between the base metals to form a sandwich structure of TC4 / Zr 47 Ti 29 Ni 21 V3 / TC4.

[0074] Step 3: The lap joint and butt joint specimens were placed in a vacuum brazing furnace, and the furnace chamber was evacuated. After the vacuum degree was less than 5×10 -3 Pa, it was heated at a heating rate of 10 K / min to 1233 K (960 °C), then held for 30 min, and after welding, the specimens were taken out after cooling to room temperature with the furnace.

[0075] Step 4: Electron probe microanalysis (EPMA) was used to analyze the microstructure of the TC4 / Zr 47 Ti 29 Ni 21 V3 / TC4 joint. The backscattered electron image of the joint is as Figure 15 shown. There are no defects such as pores and cracks in the joint, achieving good metallurgical bonding. The brazing seam area is mainly lamellar structure.

[0076] Step 5: A universal testing machine was used to test the tensile shear properties of the TC4 / Zr 47 Ti 29 Ni 21 V3 / TC4 lap joint, and its tensile shear strength was 468 MPa.

[0077] Step 6: Process the TC4 / Zr 47 Ti 29 Ni 21 The butt joint of V3 / TC4 is processed into a standard U-notch specimen with dimensions of 5 mm × 10 mm × 55 mm, and its Charpy impact toughness is tested using an impact testing machine, and its impact toughness can be as high as 20.5 J / cm 2 . The results show that using Zr 47 Ti 29 Ni 21 V3 amorphous alloy as the filler metal to braze TC4 titanium alloy, the joint has both high strength and high toughness.

Claims

1. A Zr-Ti-Ni-V-based amorphous alloy and an amorphous / nanocrystalline composite alloy, characterized in that: The chemical composition expression of the alloy is: Zr a Ti b Ni c V d , where a, b, c, and d respectively represent the atomic percentages of the corresponding components Zr, Ti, Ni, and V, and a + b + c + d = 100; Alloy ribbons with amorphous structure or amorphous / nanocrystalline composite structure are prepared by melt spinning quenching method; When the chemical composition of the alloy is 47≤a≤50, 25<b≤40, 15≤c≤30, 2≤d≤6, the alloy ribbons with a thickness of 10≤thickness<40μm have an amorphous structure, and the alloy ribbons with a thickness of 40~80μm have an amorphous / nanocrystalline composite structure; when the chemical composition of the alloy is 50<a≤65, 20≤b≤55, 15≤c≤20, 2≤d≤6 or 40≤a≤45, 40<b≤55, 15≤c≤20, 2≤d≤6, the alloy ribbons with a thickness of 10≤thickness<20μm have an amorphous structure, and the alloy ribbons with a thickness of 20~80μm have an amorphous / nanocrystalline composite structure.

2. The Zr-Ti-Ni-V-based amorphous alloy and amorphous / nanocrystalline composite alloy according to claim 1, characterized in that: The size of the nanocrystals in the amorphous / nanocrystalline composite structure is 5~100nm.

3. The Zr-Ti-Ni-V based amorphous alloy and amorphous / nanocrystalline composite alloy according to claim 1, characterized in that: The liquidus temperature of the alloy is 900K~1400K.

4. A preparation method for Zr-Ti-Ni-V-based amorphous alloy and amorphous / nanocrystalline composite alloy, characterized in that, It is used to prepare the Zr-Ti-Ni-V series amorphous alloy and amorphous / nanocrystalline composite alloy according to any one of claims 1-3, including the following steps: Step 1: Convert the characteristic components of the alloy from atomic percentage to mass percentage, and weigh the elemental metal raw materials of each component with a balance for alloy batching; Step 2: Put the raw materials proportioned in Step 1 into a vacuum arc melting furnace, evacuate to make the vacuum degree in the furnace reach 3×10 −3 ~5×10 −3 Pa, and then fill with argon as the protective gas; adjust the arc current to 100 - 150 A, repeatedly melt the alloy ingot 3 - 5 times to ensure the uniformity of the alloy composition, and take out the alloy ingot after it cools to room temperature with the furnace to obtain the master alloy ingot; Step 3: Mechanically crush the master alloy ingot into small pieces, take 3 - 5 g from them and place them in a quartz tube with an opening at the bottom. Put the quartz tube and the alloy raw materials as a whole into the melt spinning quenching equipment, and adjust the distance between the opening at the bottom of the quartz tube and the surface of the copper wheel to 1 - 2 mm; evacuate to make the vacuum degree in the cavity of the melt spinning quenching equipment reach 2×10 −2 Pa, and then fill it with argon as the protective gas; set the rotational speed of the copper wheel to 10 - 60 m / s, the injection pressure to 0.02 - 0.05 MPa, and the induction heating current to 5 - 10 A; use the induction heating method to melt the master alloy, and then use argon to inject the melted alloy from the opening at the bottom of the quartz tube onto the high-speed rotating copper wheel, so as to obtain a continuous and flexible Zr-Ti-Ni-V-based amorphous alloy or amorphous / nanocrystalline composite alloy ribbon.

5. The Zr-Ti-Ni-V-based amorphous alloy and amorphous / nanocrystalline composite alloy according to any one of claims 1-3, characterized in that, It is used as a kind of brazing material.

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