Multi-component titanium-based amorphous alloy, preparation method and application of multi-component titanium-based amorphous alloy as connecting material

Abstract

The invention relates to the field of alloys, and discloses a multi-component titanium-based amorphous alloy, a preparation method and application of the multi-component titanium-based amorphous alloy as a connecting material. The composition of the multi-component titanium-based amorphous alloy disclosed by the invention is Ti Zr Cu < c > Ni < d > Fe < e > Co < f > H < f > g, wherein a is equal to 35 to 40, b is equal to 25 to 30, c is equal to 13.75 to 17.25, d is equal to 2.75 to 7.25, e is equal to 2.75 to 7.25, f is equal to 2.75 to 7.25, g is equal to 2.75 to 7.25, and a + b + c + d + e + f + g is equal to 100. The multi-component titanium-based amorphous alloy has good room-temperature machinability, and has excellent connection strength when being used as a connection material.

Description

Technical Field

[0001] This invention relates to the field of alloys, and more particularly to a multi-component titanium-based amorphous alloy, its preparation method, and its application as a connecting material. Background Technology

[0002] Compared with traditional crystalline materials, amorphous alloys have many unique properties, such as metastable structure with long-range disordered atomic arrangement. Therefore, they exhibit high strength, high wear resistance, high corrosion resistance, and good magnetic properties. These excellent properties have made them a new type of metallic material that has attracted widespread attention in the industrial field. Among them, the use of amorphous alloys as connecting materials is one of the important applications of amorphous alloys.

[0003] Traditional titanium-based bonding materials used in high-temperature alloy joining are mostly in the form of powder, paste, or tape. These materials are limited by the high oxygen content resulting from the powdering process, and for complex structures such as right-angle welds and honeycomb structures, the bonding material cannot completely cover the base material, posing a threat to the metallurgical bonding safety of the materials.

[0004] Existing titanium-based alloy joining materials typically incorporate a significant amount of Cu and Ni as the main elements to lower the melting point. However, the introduction of Cu and Ni causes the titanium alloy joint to generate a large number of brittle intermetallic compounds (such as Ti-Ni phase and Ti-2Cu phase) during the joining process, thereby reducing the mechanical properties of the joint (Research Status of High-Temperature Brazing Alloys Commonly Used in Aerospace - Precision Forming Engineering; 10.13567 / j.cnki.issn1009-9964.2024.03.010).

[0005] Therefore, there is an urgent need to develop a multi-component titanium-based amorphous alloy connecting material that possesses excellent room-temperature machinability as well as superior material bonding strength. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a multi-component titanium-based amorphous alloy, its preparation method, and its application in metallurgical bonding. The multi-component titanium-based amorphous alloy of this invention exhibits good room-temperature machinability and excellent bonding strength when used as a bonding material.

[0007] The specific technical solution of the present invention includes: In a first aspect, the present invention provides a multi-component titanium-based amorphous alloy, the composition of which is Ti a Zr b Cu c Ni d Fe e Co f Hf ga, b, c, d, e, f, and g represent the mass percentages of each element, where a = 35–40, b = 25–30, c = 13.75–17.25, d = 2.75–7.25, e = 2.75–7.25, f = 2.75–7.25, and g = 2.75–7.25, and a + b + c + d + e + f + g = 100. The multi-element titanium-based amorphous alloy is prepared by melt spin quenching.

[0008] Existing titanium-based joining materials generally incorporate significant amounts of Cu and Ni elements to lower the joining temperature. However, the introduction of Cu and Ni leads to the formation of numerous brittle intermetallic compounds (such as Ti-Ni and Ti-2Cu phases) during the joining process, reducing the mechanical properties of the joint. Therefore, this invention comprehensively considers factors such as the amorphous alloy's forming ability, entropy effect, and the joining temperature and strength of the joining material. Through raw material improvements (replacing some Cu and Ni with Fe, Co, and Hf elements) and process improvements (using melt spin quenching), a multi-component titanium-based amorphous alloy with good room-temperature machinability and higher joining strength is obtained. Specifically: Regarding raw material improvement: In this invention, Cu and Ni form a eutectic with Ti and Zr to obtain a low-melting-point alloy bonding material. Based on this, appropriate amounts of Fe, Co, and Hf are added to the refractory multi-component alloy (Ti-Zr-Cu-Ni). Specifically, Fe and Co have negative enthalpies of mixing with Ti and Zr, which can increase the degree of atomic size mismatch among the constituent elements, thereby improving the amorphous forming ability of the titanium-zirconium-based alloy, reducing the eutectoid transformation rate of the titanium alloy, reducing the brittleness of the joint, and improving the bonding strength. Hf works similarly; it has a large negative enthalpy of mixing with Cu, Ni, Fe, and Co. The significant atomic size difference between Hf and Co and Ni can improve the amorphous forming ability of the titanium-zirconium-based bonding material, while also having a good strengthening effect on the β-solid solution of the titanium alloy. Furthermore, the added elements Fe, Co, and Hf have good wettability with the titanium alloy (the bonding object).

[0009] Furthermore, this invention has found that the contents of Fe, Co, and Hf are also crucial. If the contents of Fe, Co, and Hf are too low (<2.75%), they are insufficient to produce a significant entropy effect and mixing enthalpy advantage, resulting in insufficient interfacial segregation effect, weak amorphous formation ability, and poor suppression of brittle phases. Conversely, if the contents of Fe, Co, and Hf are too high (>7.25%), Fe / Co / Hf-rich phases are easily formed, which may precipitate Fe-Ti, Co-Ti, or Hf-Cu intermetallic compounds, becoming crack sources, increasing brittleness, and reducing joint toughness.

[0010] Regarding improvements in the manufacturing process: This invention employs a melt spin quenching method. During the fabrication of amorphous alloy strips, rapid cooling can suppress the precipitation and growth of brittle crystalline phases in titanium-based materials, thereby enabling the titanium-based amorphous alloy bonding material to possess better plasticity at room temperature than its corresponding crystalline counterpart. Rapid cooling of amorphous alloys allows for the mixing of various elements, introducing "structural disorder" to obtain alloy materials with superior performance.

[0011] In summary, on the one hand, based on the idea of ​​entropy regulation, this invention introduces "structural order" while modulating "chemical order," developing a novel alloy joining material that combines the excellent characteristics of both amorphous alloys and multi-component alloys. On the other hand, by utilizing rapid cooling technology, the problem of preparing strips with good plasticity at room temperature from crystalline alloys can be solved, obtaining a multi-component titanium-based amorphous system that can meet the requirements of complex structural joining.

[0012] Preferably, the multi-component titanium-based amorphous alloy is a strip with a thickness of 40-80 μm and a width of 15-25 mm.

[0013] Secondly, the present invention provides a method for preparing the above-mentioned multi-component titanium-based amorphous alloy, which includes the following steps: 1) mixing and melting the raw materials to obtain a master alloy ingot.

[0014] 2) After crushing the master alloy ingot, a multi-component titanium-based amorphous alloy is prepared by melt spin quenching.

[0015] Preferably, in step 1), each elemental substance is pre-treated with a surface deoxidation layer.

[0016] Preferably, in step 1), after adding the elemental substances to the melting device in order of melting point from low to high, a vacuum is first drawn before melting, and then inert gas is used to replace the gas.

[0017] Further preferably, in step 1), the vacuuming is performed to a vacuum level of ≤3×10-3 Pa.

[0018] Preferably, in step 1), the melting is electric arc melting, with a melting current of 200-300A and a melting time of 110-130 seconds per cycle, repeated multiple times to obtain a master alloy ingot. Preferably, in step 2), the master alloy ingot is crushed and placed into a crucible, and a vacuum is drawn in a melt quenching device and filled with inert gas; the alloy is heated to melt, and when the temperature exceeds the melting point of 100-290°C, the melt is sprayed onto the surface of a rotating copper roller by the pressure of the inert gas to form a continuous amorphous ribbon.

[0019] Controlling the spray temperature to be 100-290℃ above the alloy melting point can significantly reduce melt viscosity, improve fluidity, and ensure that the melt can be evenly spread across the roller surface. On the other hand, it also increases the initial temperature difference between the melt and the cooling roller, raising the critical cooling rate and increasing the system's tendency to form amorphous materials. If the temperature is too low (<100℃), the melt will have high viscous resistance, making it difficult to spread evenly in a very short time during high-speed spraying, easily leading to uneven strip thickness, surface wrinkles, and strip breakage. If the temperature is too high (>290℃), it will exacerbate the volatilization of low-melting-point elements, causing deviations in strip composition and reducing the ability to form amorphous materials; excessively high temperatures also increase the risk of reaction between the melt and crucible material, introducing impurities that contaminate the alloy liquid; overheated melts have extremely high fluidity, which may cause splashing during spraying and contact with the roller surface, greatly increasing the difficulty of forming and also increasing the pressure on the cooling system.

[0020] Preferably, in step 2), the master alloy ingot is crushed and placed into a crucible. The crucible is then evacuated to ≤8×10-3Pa in a melt quenching device, and inert gas is introduced to make the cavity pressure reach 20-80kPa. The linear speed of the copper roller is adjusted to 20-45m / s, and the alloy is heated to melt. When the temperature exceeds the melting point of 100-290℃, the melt is sprayed onto the surface of the rotating copper roller with an inert gas pressure of 20-80kPa to form a continuous amorphous ribbon.

[0021] On the one hand, controlling the pressure difference between 20-80 kPa during strip spraying provides sufficient kinetic energy to the melt, ensuring close and uniform contact with the roller surface and rapid cooling. On the other hand, appropriate pressure also balances the melt's fluidity and cooling rate, ensuring stable molding. If the spraying pressure is too low (<20 kPa), the kinetic energy of the melt flow onto the roller surface is small, potentially leading to insufficient contact or gaps between the melt and the cooling roller. This significantly reduces heat transfer efficiency and the actual cooling rate, causing strip crystallization and severely affecting the performance of amorphous strips. If the spraying pressure is too high (>80 kPa), the excessive kinetic energy of the melt jet causes splashing upon contact with the roller surface, making it difficult to form a uniform thin layer and damaging the strip's molding. Sustained excessive pressure intensifies the impact on the cooling roller surface, increasing the risk of wear and damage.

[0022] On the other hand, a sufficient copper roller linear speed (20-45 m / s) can rapidly remove the heat from the melt after it contacts the roller, reaching the critical cooling rate, thereby inhibiting crystal nucleation and growth. It also ensures good matching with the melt's spray pressure and temperature, resulting in amorphous ribbons with bright surfaces and neat edges. If the linear speed is too low (<20 m / s), the cooling time of the melt on the copper roller surface is relatively prolonged, and the actual cooling rate is lower than the critical cooling rate required for the alloy to form amorphous material. This leads to excessive ribbon thickness, crystallization, increased brittleness, and decreased formability and surface quality. If the linear speed is too high (>45 m / s), the melt cools extremely rapidly, forming ultra-thin ribbons, which easily results in excessive porosity on the ribbon surface, breakage, and inability to form continuous thin ribbons.

[0023] Preferably, in step 2), the injection pressure of the inert gas is the pressure difference between the pressure of the gas storage tank (120-160 kPa) and the pressure of the cavity (20-80 kPa).

[0024] Preferably, in step 2), the distance between the surface of the copper roller and the crucible nozzle is 1 to 3 mm.

[0025] Thirdly, the present invention provides the application of the above-mentioned multi-component titanium-based amorphous alloy as a connecting material, which can be used for connecting similar or dissimilar materials in titanium alloys, metallized ceramics and stainless steel.

[0026] The multi-component titanium-based amorphous alloy of this invention exhibits strong amorphous forming ability, low brittle intermetallic compounds, and good mechanical properties of the metallurgical joint. It demonstrates excellent wettability and connection strength with similar or dissimilar materials such as titanium alloys, metallized ceramics, and stainless steel. Furthermore, the multi-component titanium-based amorphous alloy of this invention exhibits good room-temperature machinability, allowing for repeated folding without fracture at room temperature, making it suitable for complex structural connections. The TA17 titanium alloy joint has a tensile strength ≥597MPa, elongation after fracture ≥0.4%, and reduction of area ≥1.5%.

[0027] Preferably, the temperature of the connection is 950-1100℃, and the heat preservation time is 5-20 minutes.

[0028] Compared with the prior art, the beneficial effects of the present invention are: (1) By replacing some of Cu and Ni with Fe, Co and Hf elements, the present invention can improve the degree of mismatch of atomic size of constituent elements, thereby improving the amorphous forming ability of titanium zirconium-based alloy, reducing the eutectoid transformation rate of titanium alloy, reducing the brittleness of joint, and improving the connection strength; at the same time, Fe, Co and Hf also have good wettability with titanium alloy (joint object).

[0029] (2) The present invention uses the melt spin quenching method to prepare amorphous alloy strips. Through rapid cooling, the precipitation and growth of brittle crystalline phases in titanium-based materials can be suppressed, thereby giving titanium-based amorphous alloy connecting materials better plasticity at room temperature than the corresponding crystalline materials.

[0030] (3) Based on the idea of ​​entropy regulation, this invention introduces "structural order" while modulating "chemical order" to develop a novel alloy connecting material that combines the excellent characteristics of amorphous alloys and multi-component alloys. At the same time, this invention utilizes rapid cooling technology to solve the problem that it is difficult to prepare strips with good plasticity at room temperature from crystalline alloys, and obtains a multi-component titanium-based amorphous system that can meet the requirements of complex structural connections. Attached Figure Description

[0031] Figure 1 The image shows a physical sample of the multi-component titanium-based amorphous alloy TiZrCuNiFeCoHf obtained in Example 1.

[0032] Figure 2 The X-ray diffraction patterns of four representative products obtained in Example 1 and Comparative Examples 1-1 to 1-3 are shown.

[0033] Figure 3 This is a schematic diagram of the connection structure of the product obtained in Example 1.

[0034] Figure 4 The image shows the SEM topography of the connector of the product obtained in Example 1.

[0035] Figure 5 The image shows the elemental diffusion diagram of the connector of the product obtained in Example 1 using EDS energy dispersive spectroscopy. Detailed Implementation

[0036] The present invention will be further described below with reference to embodiments.

[0037] General Implementation Examples Firstly, a multi-component titanium-based amorphous alloy, the composition of which is Ti a Zr b Cu c Ni d Fe e Co f Hf g a, b, c, d, e, f, and g represent the mass percentages of each element, where a = 35–40, b = 25–30, c = 13.75–17.25, d = 2.75–7.25, e = 2.75–7.25, f = 2.75–7.25, and g = 2.75–7.25, and a + b + c + d + e + f + g = 100.

[0038] Preferably, the multi-component titanium-based amorphous alloy is prepared by melt spin quenching.

[0039] Preferably, the multi-component titanium-based amorphous alloy is a strip with a thickness of 40-80 μm and a width of 15-25 mm.

[0040] Secondly, a method for preparing the above-mentioned multi-component titanium-based amorphous alloy includes the following steps: 1) Mix and melt the raw materials to obtain the master alloy ingot.

[0041] Preferably, in step 1), each elemental substance is pre-treated with a surface deoxidation layer.

[0042] Preferably, in step 1), after adding the elemental substances to the melting device in order of melting point from low to high, a vacuum is first drawn before melting, and then inert gas is used to replace the gas.

[0043] Further preferably, in step 1), the vacuuming is performed to a vacuum level of ≤3×10-3 Pa.

[0044] Preferably, in step 1), the melting is electric arc melting, with a melting current of 200-300A and a melting time of 110-130 seconds per cycle, and the melting is repeated multiple times to obtain a master alloy ingot.

[0045] 2) After crushing the master alloy ingot, a multi-component titanium-based amorphous alloy is prepared by melt spin quenching.

[0046] Preferably, in step 2), the master alloy ingot is crushed and placed into a crucible, and a vacuum is drawn in a melt quenching device and filled with inert gas; the alloy is heated to melt, and when the temperature exceeds the melting point of 100-290°C, the melt is sprayed onto the surface of a rotating copper roller by the pressure of the inert gas to form a continuous amorphous ribbon.

[0047] Preferably, in step 2), the master alloy ingot is crushed and placed into a crucible. The crucible is then evacuated to ≤8×10-3Pa in a melt quenching device, and inert gas is introduced to make the cavity pressure reach 20-80kPa. The linear speed of the copper roller is adjusted to 20-50m / s, and the alloy is heated to melt. When the temperature exceeds the melting point of 100-290℃, the melt is sprayed onto the surface of the rotating copper roller with an inert gas pressure of 20-80kPa to form a continuous amorphous ribbon.

[0048] Preferably, in step 2), the injection pressure of the inert gas is the pressure difference between the pressure of the gas storage tank (120-160 kPa) and the pressure of the cavity (20-80 kPa).

[0049] Preferably, in step 2), the distance between the surface of the copper roller and the crucible nozzle is 1 to 3 mm.

[0050] Thirdly, the aforementioned multi-component titanium-based amorphous alloys can be used as connecting materials to join similar or dissimilar materials in titanium alloys, metallized ceramics, and stainless steel.

[0051] Preferably, the temperature of the connection is 950-1100℃, and the heat preservation time is 5-20 minutes.

[0052] Specific embodiments and comparative examples Example 1 Ti 37.5 Zr 27.5 Cu 15 Preparation of Ni5Fe5Co5Hf5 multi-component titanium-based amorphous alloy connecting strip: S1-1, Master Alloy Formulation Using Ti, Cu, Ni, Fe, Co, Hf metal particles and crystalline Zr rods as raw materials, the purity of each raw material is >99.9%. The surface of the raw materials is treated with acid washing to remove the oxide layer and impurities. Specifically, the raw materials are soaked in a 5% mass fraction dilute hydrochloric acid solution for 5 minutes, and then soaked in a 2% mass fraction NaHCO3 solution for 3 minutes to neutralize the acid on the surface. Then, they are rinsed with ethanol and ultrasonically cleaned in ethanol for 5 minutes. After cleaning, they are dried with lint-free paper and weighed according to the mass percentages of Ti 37.5%, Zr 27.5%, Cu 15%, Ni 5%, Fe 5%, Co 5%, and Hf 5%.

[0053] S1-2, smelting master alloy The raw materials prepared in S1-1 are arranged in order of melting point in the water-cooled copper crucible of the non-consumable vacuum arc furnace, with the higher melting point Hf on top and the lower melting point Cu on the bottom. The vacuum level inside the furnace is first evacuated to 8 × 10⁻⁶. -3 The furnace is then filled with inert argon gas to create a vacuum of 50 kPa, and this purging process is repeated three times. Next, under an argon atmosphere with a vacuum of 60 kPa, an arc is ignited using a current of 100 A. The current is then increased to 250 A to first melt the titanium ingot in the oxygen-absorbing station to further remove oxygen from the furnace. Then, the raw materials are melted, with electromagnetic stirring activated simultaneously to ensure thorough mixing of the alloy melt. Each melting cycle lasts 120 seconds. After each melting cycle, the alloy ingot is allowed to cool, flipped, and the melting process is repeated four times to obtain a uniformly mixed alloy ingot.

[0054] S1-3, Preparation of strip material The oxide layer on the surface of the S1-2 alloy ingot was removed using an angle grinder. The ingot was then mechanically crushed into blocks approximately 1 cm in diameter. 100 g of each block was weighed and placed into a boron nitride tube with a nozzle width of 1 mm and a length of 15 mm. This boron nitride tube containing the alloy blocks was then installed inside the induction heating coil of the vacuum quenching chamber, with the tube opening perpendicular to the tangent of the copper roller and 1 mm from the roller surface. The mechanical pump was turned on, and once the vacuum level in the quenching chamber reached below 10 Pa, the molecular pump was turned on to evacuate to a higher vacuum of 3 × 10⁻⁶ Pa. -3 Below Pa, argon gas is introduced for purging three times. During strip preparation, the argon pressure in the quenching chamber is 50 kPa, and the pressure in the casting gas tank is 120 kPa, meaning the argon injection pressure is 70 kPa. The copper roller is adjusted until the surface linear velocity reaches 32 m / s. The high-frequency power supply is then turned on, and the alloy block in the boron nitride tube is heated and melted using high-frequency induction heating. When obvious swaying is observed on the surface of the liquid alloy through the glass observation window at the top of the boron nitride tube, and the infrared thermometer reading is approximately 200°C above the melting point, the casting process begins. Under the action of the argon gas jet, the liquid material is sprayed onto the surface of the high-speed rotating copper roller, forming a continuous, tough, and smooth strip with a thickness of 60 μm and a width of 20 mm. The product is as follows: Figure 1 As shown.

[0055] S1-4. Strip performance analysis: The amorphous structure was studied using X-ray diffraction (XRD). The strip was laid flat on the sample stage, and the scanning angle 2θ ranged from 20° to 80° with a scanning step of 0.02° / s. Figure 2 As shown in the XRD pattern, the tape prepared by the method in Example 1 exhibits the characteristic diffuse "bun peaks" of amorphous materials, indicating that the tape obtained in Example 1 has a distinct amorphous structure. No other brittle intermetallic compounds precipitate, which explains why the amorphous tape does not fracture after repeated folding at room temperature.

[0056] S1-5. Performance testing and microstructure analysis of the joint. The strip from Example 1 was immersed in 3% hydrochloric acid for 20 seconds to remove surface organic contaminants. Then, residual acid was neutralized in a 2% NaHCO3 solution, and the strip was rinsed thoroughly with water. It was then ultrasonically cleaned in ethanol for 60 seconds and dried with lint-free paper. Samples measuring 40mm × 20mm × 4mm were prepared from the TA17 (Ti-4Al-2V) base material. The surface of the base material was polished with 60# to 3000# sandpaper, then ultrasonically cleaned with ethanol for 5 minutes. After cleaning, the sample was dried with lint-free paper and used for the connection test. The TA17 titanium alloy was welded using a butt joint method, with a butt joint area of ​​20mm × 4mm. A schematic diagram of the butt joint is shown below. Figure 3As shown. The vacuum furnace was heated from room temperature to 950°C at a heating rate of 5°C / min, held at that temperature for 10 minutes, and then the heating was stopped, allowing the furnace to cool down. During the material joining process, the vacuum level in the vacuum furnace cavity was maintained at 6 × 10⁻⁶. -3 Pa, after which the mechanical properties of the sample are tested.

[0057] The testing environment was 20℃ and 70%RH.

[0058] Comparative Example 1-1 To compare the effects of entropy, Comparative Example 1-1 used Ti as the constituent. 37.5 Zr 37.5 Cu 15 Ni 10 Quaternary titanium-based amorphous alloy strip has fewer components and lower chemical entropy.

[0059] Ti 37.5 Zr 37.5 Cu 15 Ni 10 Preparation of quaternary titanium-based amorphous alloy strip: S1-1-1, Master Alloy Formulation Using Ti, Cu, and Ni metal particles and crystalline Zr rods as raw materials, the purity of each raw material is >99.9%. The surface of the raw materials is treated with acid washing to remove the oxide layer and impurities. Specifically, the raw materials are first soaked in a 5% mass fraction dilute hydrochloric acid solution for 5 minutes, and then soaked in a 2% mass fraction NaHCO3 solution for 3 minutes to neutralize the acid on the surface. Then, they are rinsed with ethanol and ultrasonically cleaned in ethanol for 5 minutes. After cleaning, they are dried with lint-free paper and weighed according to the mass percentages of Ti 37.5%, Zr 37.5%, Cu 15%, and Ni 10%.

[0060] S1-1-2, Master alloy for smelting Arrange the prepared raw materials (S1-1-1) in order of melting point in the water-cooled copper crucible of the non-consumable vacuum arc furnace, with the higher melting point Zr on top and the lower melting point Cu on the bottom. First, evacuate the furnace to a vacuum level of 8 × 10⁻⁶. -3 The furnace is then filled with inert argon gas to create a vacuum of 50 kPa, and this purging process is repeated three times. Next, under an argon atmosphere with a vacuum of 60 kPa, an arc is ignited using a current of 100 A. The current is then increased to 250 A to first melt the titanium ingot in the oxygen-absorbing station to further remove oxygen from the furnace. Then, the raw materials are melted, with electromagnetic stirring activated simultaneously to ensure thorough mixing of the alloy melt. Each melting cycle lasts 120 seconds. After each melting cycle, the alloy ingot is allowed to cool, flipped, and the melting process is repeated four times to obtain a uniformly mixed alloy ingot.

[0061] S1-1-3, Strip Preparation The oxide layer on the surface of the S1-1-2 alloy ingot was removed using an angle grinder. The ingot was then mechanically crushed into blocks approximately 1 cm in diameter. 100 g of each block was weighed and placed into a boron nitride tube with a nozzle width of 1 mm and a length of 15 mm. This boron nitride tube containing the alloy blocks was then installed inside the induction heating coil of the vacuum quenching chamber, with the tube opening perpendicular to the tangent of the copper roller and 1 mm from the roller surface. The mechanical pump was turned on, and once the vacuum level in the quenching chamber reached below 10 Pa, the molecular pump was turned on to evacuate to a higher vacuum of 3 × 10⁻⁶ Pa. -3 Below Pa, argon gas is introduced for purging three times. During strip preparation, the argon pressure in the quenching chamber is 50 kPa, and the pressure in the casting gas storage tank is 120 kPa, meaning the argon injection pressure is 70 kPa. The copper roller is adjusted until the surface linear velocity reaches 30 m / s. The high-frequency power supply is then turned on, and the alloy block in the boron nitride tube is heated and melted using high-frequency induction heating. When obvious swaying is observed on the surface of the liquid alloy through the glass observation window at the top of the boron nitride tube, and the infrared thermometer reading is approximately 150°C above the melting point, the casting process begins. Under the action of the argon gas jet, the liquid material is sprayed onto the surface of the high-speed rotating copper roller, forming a continuous, tough, and smooth strip with a thickness of 70 μm and a width of 20 mm.

[0062] S1-1-4 Strip Performance Analysis Depend on Figure 2 The XRD patterns shown indicate that the tape prepared by the method in Comparative Example 1-1 exhibits diffuse "bun peaks" characteristic of amorphous materials after X-ray diffraction, demonstrating that the tape obtained in Comparative Example 1-1 has a distinct amorphous structure.

[0063] S1-1-5. Performance testing and microstructure analysis of the joint. The strip from Comparative Example 1-1 was immersed in 3% dilute hydrochloric acid for 20 seconds to remove surface organic contaminants. Then, residual acid was neutralized with 2% alkali solution and rinsed thoroughly with water. It was then ultrasonically cleaned in ethanol for 60 seconds and dried with lint-free paper. Samples of TA17 base material, measuring 40mm × 20mm × 4mm, were prepared. The surface of the base material was polished with 60# to 3000# sandpaper, then ultrasonically cleaned with ethanol for 5 minutes. After cleaning, the sample was dried with lint-free paper for use in the connection test. Butt welding of the TA17 titanium alloy was performed using a butt joint with a butt area of ​​20mm × 4mm. The lap diagram is shown below. Figure 3 As shown. The vacuum furnace was heated from room temperature to 950°C at a heating rate of 5°C / min, held at that temperature for 10 minutes, and then the heating was stopped, allowing the furnace to cool down. During the material joining process, the vacuum level in the vacuum furnace cavity was maintained at 6 × 10⁻⁶. -3 Pa, after the connection is completed, the mechanical properties of the connected specimen are tested.

[0064] The testing environment was 20℃ and 70%RH. Three sets of samples were numbered.

[0065] Comparative Examples 1-2 To compare the effects of entropy and amorphization, Comparative Examples 1-2 were selected using Ti as the constituent material. 37.5 Zr 37.5 Cu 15 Ni 10 The crystalline powders in Comparative Examples 1-2 were obtained by gas atomization powdering, and the remaining technical features were the same as those in Example 1.

[0066] Comparative Examples 1-3 The titanium-based amorphous alloy strip in Comparative Example 1-1 was heated to above the crystallization temperature, i.e., 600°C, and held at that temperature for 1 hour until it completely transformed into a crystalline state. This was used to compare the effects of entropy and amorphization. The remaining technical features were the same as in Example 1.

[0067] Example 2 The study investigated the effect of chemical entropy changes caused by the content of multiple components on the performance of the bonding material. The mass fraction percentage composition of the multi-component titanium-based amorphous alloy in Example 1 was replaced with: Ti 35%, Zr 25%, Cu 17.5%, Ni 4.5%, Fe 6%, Co 6%, Hf 6%, and the remaining technical characteristics were the same as in Example 1.

[0068] Comparative Example 2-1 The study investigated the effect of chemical entropy changes caused by the content of multiple components on the performance of the bonding material. The mass fraction percentage components of the multi-component titanium-based amorphous alloy in Example 2 were replaced with: Ti 35%, Zr 25%, Cu 25%, Ni 12%, Fe 1%, Co 1%, Hf 1%, and the remaining technical characteristics were the same as in Example 1.

[0069] Comparative Example 2-2 The study investigated the effect of chemical entropy changes caused by the content of multiple components on the performance of the bonding material. The mass fraction percentage composition of the multi-component titanium-based amorphous alloy in Example 2 was replaced with: Ti 35%, Zr 25%, Cu 10%, Ni 3%, Fe 9%, Co 9%, Hf 9%, and the remaining technical characteristics were the same as in Example 1.

[0070] Example 3 To study the effect of constant chemical entropy and different spraying pressure on the properties of the bonding material, the spraying pressure in the preparation process of the multi-component titanium-based amorphous alloy in Example 1 was replaced with an argon pressure of 30 kPa in the spin quenching chamber and a pressure of 130 kPa in the spraying gas storage tank, i.e., an argon injection pressure of 100 kPa. The remaining technical features are the same as in Example 1.

[0071] Example 4 This study investigates the effect of different spray casting melt temperatures on the properties of bonding materials under constant chemical entropy. The spray casting temperature in the preparation process of the multi-component titanium-based amorphous alloy in Example 1 was replaced with an infrared thermometer reading that was 300°C above the melting point. All other technical features were the same as in Example 1.

[0072] Example 5 To study the effect of constant chemical entropy on material properties by varying copper roller speed (i.e., cooling rate), the copper roller speed in the preparation process of the multi-component titanium-based amorphous alloy in Example 1 was replaced with 50 m / s, while the remaining technical features were the same as in Example 1.

[0073] Performance testing Figure 1 This is a photograph of the multi-component titanium-based amorphous alloy prepared in Example 1. Figure 1 As can be seen, the strip is smooth and flat, with adjustable dimensions, and has good room temperature processability.

[0074] Figure 2 These are the X-ray diffraction patterns of the multi-component titanium-based amorphous alloy prepared in Example 1 and representative products obtained from Comparative Examples 1-1 to 3. From... Figure 2 As can be seen, the spectra of Example 1 and Comparative Example 1-1 show diffuse peaks characteristic of amorphous materials, indicating that the structure of the strip is amorphous. Example 1 obtained a better full width at half maximum (FWHM), which also means that the amorphous degree of this thin strip is higher, and the increase in chemical entropy promotes the amorphous formation ability. Comparative Examples 1-2 and 1-3, on the other hand, show a completely crystalline structure.

[0075] Figure 4 This is the SEM morphology of the multi-component titanium-based amorphous alloy joint to TA17 prepared in Example 1. It can be seen that the joint maintains good plasticity while possessing excellent hardness, and has a fine microstructure.

[0076] Figure 5 This is the EDS spectrum of the multi-component titanium-based amorphous alloy joint to TA17 prepared in Example 1. It can be seen that the elements diffuse uniformly around the joint, exhibiting good wettability. The added elements Fe, Co, and Hf all demonstrate excellent wettability to the base material TA17. Simultaneously, the entropy effect of the multi-component alloy forms a single-phase solid solution without phase separation, thus improving the joint strength.

[0077] The tensile strength, elongation after fracture, and reduction of area of ​​the TA17 connector were tested on the samples of each embodiment and comparative example. Each case was tested 3 times, and the test results are shown in Table 1.

[0078] Table 1 As shown in Table 1, the tensile strength of the multi-component titanium-based amorphous alloy joint to TA17 prepared in Example 1 reached 587-613 MPa, with an elongation after fracture of 0.4% and a reduction of area of ​​1.5%.

[0079] The tensile strength (average 602.7 MPa) of Example 1 (seven-component amorphous ribbon) was significantly higher than that of Comparative Example 1-1 (quaternary amorphous ribbon, 508 MPa), Comparative Example 1-2 (crystalline powder, 490 MPa), and Comparative Example 1-3 (crystalline ribbon, 494.7 MPa), and its elongation after fracture (0.4%) and reduction of area (1.5%) were also superior. This is because Example 1 enhances amorphous formation capability through the entropy effect of the seven-component system (Ti-Zr-Cu-Ni-Fe-Co-Hf), and the negative mixing enthalpy and atomic size mismatch of Fe, Co, and Hf suppress the precipitation of brittle phases. In contrast, Comparative Example 1 has fewer components, lower chemical entropy, and weaker amorphous stability. Comparative Examples 1-2 (powder) and 1-3 (crystallization treatment) exhibited a large number of brittle crystalline phases in their crystalline structures, and the powder had high oxygen content and poor filling properties, resulting in a significant decrease in joint strength.

[0080] In Example 2, when the Fe, Co, and Hf content is controlled within the range of 2.75% to 7.25%, performance optimization can be achieved through the synergistic effect of multiple components. This content range can fully utilize the entropy effect and negative mixing enthalpy advantage of multiple components. The atomic size mismatch between Fe, Co, and Hf and Ti and Zr (e.g., the atomic radius of Hf is 15% larger than that of Ti) and the negative mixing enthalpy (e.g., the mixing enthalpy of Hf and Cu is about -35 kJ / mol) inhibit the precipitation of brittle intermetallic compounds (Ti-Ni, Ti-Cu phase, etc.) and promote the formation of amorphous single-phase structure. At the same time, the elements at this content have good wettability with the titanium alloy base material. The strengthening effect of Hf on β-Ti solid solution improves the joint strength, and the threshold for precipitation of Fe / Co / Hf-rich phase is not reached, avoiding the generation of crack sources. This makes the amorphous strip have both high connection strength and room temperature machinability.

[0081] In Comparative Example 2-1, when the contents of Fe, Co, and Hf are below 2.75%, the multi-element entropy effect and mixing enthalpy advantage are insufficient, making it impossible to effectively break the atomic arrangement order. The amorphous formation ability is weak, and brittle phases such as Ti-Ni are easily precipitated. Furthermore, the poor interfacial segregation effect leads to a decrease in wettability with the base material, insufficient metallurgical bonding, and a significant reduction in joint strength. In contrast, in Comparative Example 2-2, when the contents of Fe, Co, and Hf are above 7.25% (9%), the elements exceed the solid solution limit, easily forming intermetallic compounds such as Fe-Ti, Co-Ti, and Hf-Cu. These brittle phases become crack sources, the amorphous structure becomes unstable, the strip brittleness increases, and the room temperature processability and joint toughness deteriorate.

[0082] The tensile strength of Examples 2-5 was lower than that of Example 1 (602.7 MPa). Specifically, Example 2 (541.7 MPa) may have precipitated a small amount of intermetallic compounds due to the Fe / Co / Hf content being close to the upper limit (6%). Example 3 (579 MPa) suffered from excessively high casting pressure (100 kPa), leading to molten splashing and uneven strip material. Example 4 (567.7 MPa) experienced excessively high overheating temperature (300°C), causing the volatilization of low-melting-point elements. Example 5 (534 MPa) had excessively high copper roller speed (50 m / s), resulting in an excessively thin strip and increased surface defects. These parameters deviated from the optimal selection in Example 1, leading to a decrease in the integrity of the amorphous structure or the precipitation of brittle phases, ultimately reducing the joint strength.

Claims

1. A multi-component titanium-based amorphous alloy, characterized in that: Composition is Ti a Zr b Cu c Ni d Fe e Co f Hf g Where: a=35~40, b=25~30, c=13.75~17.25, d=2.75~7.25, e=2.75~7.25, f=2.75~7.25, g=2.75~7.25, and a+b+c+d+e+f+g=100.

2. The multi-component titanium-based amorphous alloy according to claim 1, characterized in that: The multi-component titanium-based amorphous alloy is a strip with a thickness of 40~80 µm and a width of 15-25 mm.

3. A method for preparing a multi-component titanium-based amorphous alloy according to claim 1 or 2, characterized in that... include: 1) Mix and melt the raw materials to obtain a master alloy ingot; 2) After crushing the master alloy ingot, a multi-component titanium-based amorphous alloy is prepared by melt spin quenching.

4. The preparation method according to claim 3, characterized in that: In step 1), after adding the elemental substances to the melting device in order of melting point from low to high, a vacuum is first drawn before melting, and then inert gas is used to replace the gas.

5. The preparation method according to claim 3 or 4, characterized in that: In step 1), the melting is electric arc melting, with a melting current of 200~300 A and a melting time of 110-130 seconds / cycle. The melting is repeated multiple times to obtain the master alloy ingot.

6. The preparation method according to claim 3, characterized in that: In step 2), the master alloy ingot is crushed and placed into a crucible. A vacuum is drawn in the melt quenching equipment and inert gas is introduced. The alloy is heated to melt. When the temperature exceeds the melting point of 100~290℃, the melt is sprayed onto the surface of the rotating copper roller by the pressure of the inert gas to form a continuous amorphous ribbon.

7. The preparation method according to claim 6, characterized in that: In step 2), the master alloy ingot is crushed and placed into a crucible. The vacuum is evacuated to ≤8×10⁻³ Pa in the melt quenching equipment, and inert gas is introduced to make the cavity pressure reach 20~80kPa. The linear speed of the copper roller is adjusted to 20~45 m / s, and the alloy is heated to melt. When the melting point exceeds 100~290℃, the melt is sprayed onto the surface of the rotating copper roller with an inert gas pressure of 20~80kPa to form a continuous amorphous ribbon.

8. The preparation method according to claim 6 or 7, characterized in that: In step 2), the distance between the surface of the copper roller and the crucible nozzle is 1~3 mm.

9. The application of the multi-component titanium-based amorphous alloy according to claim 1 or 2, or the multi-component titanium-based amorphous alloy obtained by the preparation method according to any one of claims 3-8, as a connecting material, characterized in that: Used for joining similar or dissimilar materials in titanium alloys, metallized ceramics, and stainless steel.

10. The preparation method according to claim 9, characterized in that: The temperature of the connection is 950-1100℃, and the heat preservation time is 5-20 min.

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