Method for preparing high-performance copper-titanium alloy using aerosol jet printing technology

Abstract

The present invention discloses a method for preparing a high-performance copper-titanium alloy using aerosol jet printing technology. The method comprises the following steps: first, evenly mixing refined titanium powder with a copper salt solution; then, dropping a reducing agent solution into the mixture solution, and then performing a reduction reaction to copper-plate the titanium powder surface until the titanium powder surface is completely coated with copper; then, atomizing the mother liquor to form droplets, which are transported to a print head via a carrier gas; the carrier gas, the constraining gas, and the droplets together form an aerosol jet, which is ejected from the print head. The aerosol jet is sprayed onto a substrate for aerosol jet printing to obtain copper-coated titanium powder; then, the copper-coated titanium powder is subjected to a reduction reaction to obtain a high-performance copper-titanium alloy. The present invention forms an aerosol using aerosol technology, generates a copper-coated titanium powder structure in situ during the flight of the aerosol, prepares micron-sized copper-coated titanium, and then converts it into a copper-titanium alloy through heat treatment, thereby preparing a high-strength copper-titanium alloy while ensuring mechanical and electrical properties.

Description

Technical Field

[0001] The present invention relates to the field of chemical synthesis, and in particular to a method for preparing a high-performance copper-titanium alloy by using an aerosol jet printing technology. Background Art

[0002] Copper, due to its excellent electrical and thermal conductivity, plays a core role in the manufacture of electronic components and industrial components. Among them, copper-titanium alloy, as an outstanding representative of copper-based materials, exhibits superior mechanical properties and is regarded as an ideal alternative to copper-beryllium alloy, with broad market application potential. Traditionally, current-carrying components mostly use copper-beryllium alloy, but in view of the high cost of beryllium and its long-term threat to the environment and human health, it is imperative to develop cost-effective and environmentally friendly alternative materials. Copper-titanium alloy is not only low-cost and has little environmental impact, but if it can effectively combine high electrical conductivity, excellent mechanical properties and high-temperature thermal stability, its application areas will expand from current-carrying components to multiple industries such as defense and aviation manufacturing.

[0003] The solid solution strengthening effect of titanium in copper significantly enhances the strength of the alloy. This strengthening effect becomes more pronounced as the titanium content increases, but the electrical conductivity decreases accordingly. Therefore, in order to balance mechanical and electrical properties, the titanium content is usually controlled below 5%. Current research focuses on optimizing the overall properties of copper-titanium alloys by incorporating various trace alloying elements. Although these multi-element alloys have improved mechanical properties, the thermal conductivity of the introduced elements is generally lower than that of pure copper, which increases electron scattering and may have an adverse effect on electrical conductivity. The preparation of ternary or multi-element copper-titanium alloys requires precise control of the content of each element and optimization of the final microstructure to reconcile the contradiction between mechanical and electrical properties. This process is complex, and the resulting materials often exhibit high strength but low elongation, with limited improvement in overall performance. In addition, although deformation aging treatment can improve alloy properties, oxygen impurities are easily mixed in during the process, increasing the cost burden.

[0004] The traditional manufacturing technology of copper-titanium alloys mainly includes three core processes: vacuum induction melting, vacuum arc consumable melting and mixed powder sintering technology.

[0005] Vacuum induction melting technology is characterized by a slow natural cooling process, which leads to an increase in grain size within the ingot. This larger grain size is prone to cracking during subsequent work-hardening, severely limiting the yield of finished alloy plates or ingots. Further machining steps exacerbate these losses, resulting in low final product output efficiency.

[0006] Vacuum arc consumable melting technology, by precisely controlling the droplet cooling rate and utilizing electromagnetic stirring to ensure uniform composition, can produce high-quality ingots with a fine structure and uniform composition, significantly improving the material's performance stability and overall yield. However, limitations of this technology include the difficulty of subsequent machining, coupled with high production costs, which hinder its widespread application.

[0007] Powder mixing and sintering technology offers the advantage of a high tolerance for raw materials. It achieves powder uniformity through simple physical mixing, followed by cold isostatic pressing and sintering to produce ingots. This method not only ensures uniform composition but also achieves high yield and molding efficiency, while simplifying the process. However, because the material is not molten, grain refinement is limited, resulting in products that typically exhibit larger grain sizes and relatively low mechanical strength.

[0008] Document No. 201410471560.5 discloses a CuTi-based elastic copper alloy and its preparation method. This process, involving smelting, rolling, and subsequent heat treatment, successfully produces a multi-component copper-titanium alloy with a tensile strength exceeding 1000 MPa. However, the alloy's elongation is only approximately 5%, limiting its applicability in high-temperature environments.

[0009] Document No. 201910334755.8 discloses a method for preparing ultrafine-grained copper-titanium alloy wire using powder metallurgy technology. The product is rich in nanoscale titanium particles and exhibits excellent hardness, strength, and electrical conductivity, with an elongation range of 5% to 8%. However, the preparation process is relatively complex, and the stability of the resulting alloy under high-temperature conditions still needs to be further enhanced.

[0010] In view of this, the preparation of copper-titanium alloy powder exposes problems such as insufficient product performance, inability to take into account both mechanical and electrical properties, poor high-temperature stability, high sintering temperature, and high energy consumption. There is an urgent need for a new method that is efficient, high-yield, low-cost, and environmentally friendly to meet the needs of industrial production. Summary of the Invention

[0011] In view of the shortcomings of the existing technology, the technical problem to be solved by the present invention is to provide a method for preparing high-performance copper-titanium alloy using aerosol jet printing technology.

[0012] The technical solution of the present invention to solve the above technical problem is to provide a method for preparing high-performance copper-titanium alloy using aerosol jet printing technology, which comprises the following steps:

[0013] Step 1, removing impurities from the surface of the titanium powder to obtain refined titanium powder;

[0014] Step 2: uniformly mixing the refined titanium powder obtained in step 1 with the copper salt solution to obtain a mixture solution;

[0015] Step 3, adding the reducing agent solution dropwise to the mixture solution of step 2, and then performing a reduction reaction to precipitate copper on the surface of the titanium powder, thereby copper-plating the surface of the titanium powder until the surface of the titanium powder is completely covered with copper, thereby obtaining a mother solution;

[0016] Step 4: atomizing the mother liquid obtained in step 3 to form droplets, and delivering them to an aerosol jet printing device; the droplets are delivered to a print head by a carrier gas; the carrier gas, the constraining gas, and the droplets together form an aerosol jet, which is ejected from the print head, and the aerosol jet is sprayed onto a substrate for aerosol jet printing to obtain copper-clad titanium powder;

[0017] Step 5: annealing the copper-clad titanium powder obtained in step 4 in a mixed atmosphere of hydrogen and argon to perform a reduction reaction, and then cooling to obtain a high-performance copper-titanium alloy.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] (1) The present invention forms an aerosol through aerosol technology, generating a copper-clad titanium powder structure in situ during the flight of the aerosol, preparing micron-sized copper-clad titanium, which is then converted into a copper-titanium alloy through heat treatment. The method is simple and easy to implement, significantly reduces the sintering temperature and energy consumption, and prepares a high-strength copper-titanium alloy while ensuring mechanical and electrical properties. The prepared copper-titanium alloy has a uniform texture, takes into account both mechanical and electrical properties, and has improved high-temperature stability, providing a new route for the industrial production of copper-titanium alloys.

[0020] (2) The present invention uses aerosol technology to prepare micron-sized copper-clad titanium, which has uniform particles, controllable size, and high performance. It greatly reduces the temperature during heat treatment and solves the disadvantage of low high-temperature stability of copper-titanium alloy.

[0021] (3) The aerosol particles produced by aerosol technology are small in size, which significantly increases the specific surface area and has a large surface energy, which reduces the activation energy during high-temperature reactions, thereby greatly reducing the temperature during annealing reduction.

[0022] (4) The introduction of aerosol technology in the preparation of copper-titanium alloys has changed the distribution of elements in the alloy, making it more orderly. This has greatly improved the high-temperature stability of the copper-titanium alloy and increased its service life, thereby increasing the use scenarios and expanding the market potential of the copper-titanium alloy.

[0023] (5) The present invention controls the size of the aerosol by adjusting the flow rates of the carrier gas and the restraining gas in the aerosol technology, thereby regulating the size and micromorphology of the copper-titanium alloy prepared by this method. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a SEM image of the copper-clad titanium powder prepared in Example 1 of the present invention;

[0025] Figure 2 This is a SEM image of the copper-titanium alloy prepared in Example 1 of the present invention;

[0026] Figure 3 This is a SEM image of the copper-clad titanium powder prepared in Example 3 of the present invention;

[0027] Figure 4 This is the XRD pattern of the copper-titanium alloy prepared in Example 3 of the present invention. DETAILED DESCRIPTION

[0028] The specific embodiments of the present invention are given below. The specific embodiments are only used to further illustrate the present invention and do not limit the scope of protection of the present invention.

[0029] The present invention provides a method for preparing a high-performance copper-titanium alloy using an aerosol jet printing technology (hereinafter referred to as the method), the method comprising the following steps:

[0030] Step 1, removing impurities from the surface of the titanium powder to obtain refined titanium powder;

[0031] Preferably, step 1 specifically comprises: adding titanium powder to an alkaline solution for ultrasonic stirring and then centrifuging, adding titanium powder to an organic solvent for ultrasonic stirring and then centrifuging, and adding titanium powder to anhydrous ethanol for ultrasonic stirring and then centrifuging to remove inorganic and organic impurities on the surface of the titanium powder to obtain refined titanium powder.

[0032] Preferably, in step 1, the concentration of the alkali solution is 0.5 mol / L to 3 mol / L (preferably 1.5 mol / L).

[0033] Preferably, in step 1, the alkali solution is one of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution or sodium phosphate solution (preferably sodium hydroxide solution).

[0034] Preferably, in step 1, the organic solvent is one of acetone, DMF, NMP or DMSO (preferably acetone).

[0035] Preferably, in step 1, the ultrasonic frequency is 1-2.5 MHz, the stirring speed is 100-5000 r / min, the stirring time is 10-120 min, and the temperature is room temperature.

[0036] Step 2: uniformly mixing the refined titanium powder obtained in step 1 with the copper salt solution to obtain a mixture solution;

[0037] Preferably, in step 2, in the copper salt solution, the copper salt is one of copper formate, copper sulfate, copper chloride, copper acetate or copper nitrate, and the solvent is water.

[0038] Preferably, in step 2, the mass fraction of the copper salt solution is 10-25 wt %; and the ratio of the mass of the refined titanium powder to the volume of the copper salt solution is 1 g:100-300 ml.

[0039] Preferably, in step 2, the mixing is carried out by stirring; the stirring process is: a rotation speed of 300-1000 r / min, a time of 5-30 min, and a temperature of room temperature.

[0040] Step 3: adding the reducing agent solution dropwise to the mixture solution of step 2 at room temperature, and then performing a reduction reaction to precipitate copper on the surface of the titanium powder, thereby copper-plating the surface of the titanium powder until the surface of the titanium powder is completely covered with copper, thereby obtaining a mother solution;

[0041] Preferably, in step 3, the dropping speed is 10-200 ml / min and the temperature is room temperature.

[0042] Preferably, in step 3, the concentration of the reducing agent solution is 0.5-5 mol / L (preferably 2 mol / L); and the volume ratio of the reducing agent solution to the mixture solution is 1-2:1-5 (preferably 1:3).

[0043] Preferably, in step 3, in the reducing agent solution, the reducing agent is ascorbic acid, formalin, hydrazine hydrate, glucose or hydroxylamine hydrochloride, and the solvent is water.

[0044] Preferably, in step 3, the reaction time is 2-6 h, and the reaction temperature is 40-80° C.

[0045] Step 4: Atomizing the mother liquid obtained in step 3 to form droplets, and transporting them to an aerosol jet printing device through an air pipe; the droplets are transported to a printing nozzle through a carrier gas; the carrier gas, the constraining gas, and the droplets together form an aerosol jet, which is ejected from the printing nozzle, and the flow rates of the carrier gas and the constraining gas are changed to control the width and injection speed of the aerosol jet; the aerosol jet is sprayed onto the substrate, and the solvent evaporates to form a gel. The printing height is changed to control the solvent evaporation behavior of the aerosol jet in the air, and the printing speed, the number of printing layers, and the temperature of the substrate are changed to control the oxidation process of the aerosol on the substrate, thereby obtaining copper-clad titanium powder;

[0046] Preferably, in step 4, the atomization process is ultrasonic atomization, and the ultrasonic frequency is 1.5-2.5 MHz.

[0047] Preferably, in step 4, the flow rate of the carrier gas is 200-500 sccm, and the flow rate of the confinement gas is 50-150 sccm.

[0048] Preferably, in step 4, both the carrier gas and the confinement gas are nitrogen or an inert gas, and the inert gas is argon.

[0049] Preferably, in step 4, the printing height is 5-10 mm; the printing speed is 5-50 mm / s; the number of printing layers is 50-500 layers; and the temperature of the substrate is 40-180° C.

[0050] Preferably, in step 4, the substrate is a glass plate.

[0051] Step 5: annealing the copper-clad titanium powder obtained in step 4 in a mixed atmosphere of hydrogen and argon to perform a high-temperature reduction reaction, and then cooling to obtain a high-performance copper-titanium alloy.

[0052] Preferably, in step 5, the reduction reaction temperature is 500-800° C., and the time is 3-10 h.

[0053] Preferably, in step 5, the volume ratio of hydrogen to argon is 1-25:75-99 (preferably 5:95), and the sum of the volume ratios of the two is 100%.

[0054] Example 1:

[0055] (1) Titanium powder was sequentially added to a 2 mol / L sodium hydroxide solution at room temperature for ultrasonic stirring followed by centrifugal separation, ultrasonic stirring in acetone followed by centrifugal separation, and ultrasonic stirring in anhydrous ethanol followed by centrifugal separation. The ultrasonic stirring process was performed at 200 r / min for 15 min to remove inorganic matter, titanium oxide, and other organic impurities on the surface of the titanium powder to obtain refined titanium powder.

[0056] (2) A copper salt solution with a mass fraction of 20% was prepared using copper sulfate at room temperature. 20 g of the refined titanium powder was added to 3 L of the copper salt solution, and the mixture was mixed evenly at a stirring speed of 500 r / min for 10 min to obtain a mixture solution.

[0057] (3) Prepare 1 L of ascorbic acid solution with a concentration of 2 mol / L, add it dropwise to the above mixture solution at a rate of 100 ml / min at room temperature, and then react at 40°C for 2.5 hours to allow copper to precipitate on the surface of the titanium powder, plating the titanium powder surface with copper until the surface of the titanium powder is completely covered with copper, thereby obtaining a mother solution;

[0058] (4) The mother liquid is atomized to form droplets, and the ultrasonic frequency is 1.9 MHz; the droplets are transported to the printing nozzle through the carrier gas, and the carrier gas nitrogen, the constraining gas nitrogen and the droplets together form an aerosol jet. The flow rate of the carrier gas is set to 350 sccm and the flow rate of the constraining gas is set to 85 sccm to control the width and injection speed of the aerosol jet. The aerosol jet is sprayed onto a 130°C substrate, and the printing height is 5 mm. The solvent evaporation rate of the aerosol jet in the air is controlled, and the printing speed is set to 10 mm / s and the number of printing layers is set to 100 layers to control the oxidation process of the aerosol on the substrate, and finally copper-coated titanium powder is obtained on the substrate; nitrogen is used as the carrier gas and the constraining gas;

[0059] (5) The copper-clad titanium powder was annealed in a mixed atmosphere of hydrogen and argon (the volume ratio of hydrogen to argon was 5:95) to undergo a reduction reaction at a reduction temperature of 675°C for 6.5 hours. After cooling, a high-performance copper-titanium alloy powder was obtained.

[0060] Depend on Figure 1 It can be seen that the copper-clad titanium powder is successfully coated.

[0061] Depend on Figure 2 It can be seen that the copper-titanium alloy forms a solid solution and the alloy phase is relatively uniform.

[0062] Example 2:

[0063] (1) Titanium powder was sequentially added to a 1.5 mol / L sodium hydroxide solution at room temperature for ultrasonic stirring followed by centrifugal separation, ultrasonic stirring in acetone followed by centrifugal separation, and ultrasonic stirring in anhydrous ethanol followed by centrifugal separation. The ultrasonic stirring process was performed at 200 r / min for 15 min to remove inorganic matter, titanium oxide, and other organic impurities on the surface of the titanium powder to obtain refined titanium powder.

[0064] (2) A copper salt solution with a mass fraction of 13% was prepared using copper acetate at room temperature. 30 g of the refined titanium powder was added to 3 L of the copper salt solution and mixed evenly. The stirring speed was 700 r / min for 20 min to obtain a mixture solution.

[0065] (3) Prepare 1 L of 2 mol / L hydrazine hydrate solution, add it dropwise to the above mixture solution at a rate of 150 ml / min at room temperature, and then react at 60°C for 3 h to allow copper to precipitate on the surface of the titanium powder, plating the titanium powder surface with copper until the titanium powder surface is completely covered with copper, thereby obtaining a mother solution;

[0066] (4) The mother liquid is atomized to form droplets, and the ultrasonic frequency is 2.1 MHz; the droplets are transported to the printing nozzle through the carrier gas, and the carrier gas nitrogen, the constraining gas nitrogen and the droplets together form an aerosol jet. The flow rate of the carrier gas is set to 275 sccm and the flow rate of the constraining gas is set to 110 sccm to control the width and injection speed of the aerosol jet. The aerosol jet is sprayed onto a 150°C substrate, and the printing height is 7 mm. The solvent evaporation rate of the aerosol jet in the air is controlled, and the printing speed is set to 20 mm / s and the number of printing layers is set to 150 layers to control the oxidation process of the aerosol on the substrate, and finally copper-coated titanium powder is obtained on the substrate; nitrogen is used as the carrier gas and the constraining gas;

[0067] (5) The copper-clad titanium powder is annealed in a mixed atmosphere of hydrogen and argon (the volume ratio of hydrogen to argon is 5:95) to undergo a reduction reaction at a reduction temperature of 750°C and a reduction time of 6 hours. After cooling, a high-performance copper-titanium alloy powder is obtained.

[0068] Example 3:

[0069] (1) Titanium powder was sequentially added to a 0.5 mol / L sodium hydroxide solution at room temperature for ultrasonic stirring followed by centrifugal separation, ultrasonic stirring in acetone followed by centrifugal separation, and ultrasonic stirring in anhydrous ethanol followed by centrifugal separation. The ultrasonic stirring process was performed at 200 r / min for 15 min to remove inorganic matter, titanium oxide, and other organic impurities on the surface of the titanium powder to obtain refined titanium powder.

[0070] (2) A copper salt solution with a mass fraction of 10% was prepared using copper chloride at room temperature. 100 g of the refined titanium powder was added to 1 L of the copper salt solution, and the mixture was mixed evenly at a stirring speed of 1000 r / min for 5 min to obtain a mixture solution.

[0071] (3) Prepare 333 ml of 2 mol / L hydroxylamine hydrochloride solution, add it dropwise to the above mixture solution at a rate of 50 ml / min at room temperature, and then react at 50°C for 5 h to allow copper to precipitate on the surface of the titanium powder, plating the titanium powder surface with copper until the titanium powder surface is completely covered with copper, thereby obtaining a mother solution;

[0072] (4) The mother liquid is atomized to form droplets, and the ultrasonic frequency is 2.5 MHz; the droplets are transported to the printing nozzle through the carrier gas, and the carrier gas nitrogen, the constraining gas nitrogen and the droplets together form an aerosol jet. The flow rate of the carrier gas is set to 500 sccm and the flow rate of the constraining gas is set to 150 sccm to control the width and injection speed of the aerosol jet. The aerosol jet is sprayed onto a 100°C substrate, and the printing height is 6.5 mm. The solvent evaporation rate of the aerosol jet in the air is controlled, and the printing speed is set to 25 mm / s and the number of printing layers is set to 200 layers to control the oxidation process of the aerosol on the substrate, and finally copper-coated titanium powder is obtained on the substrate; nitrogen is used as the carrier gas and the constraining gas;

[0073] (5) The copper-clad titanium powder is annealed in a mixed atmosphere of hydrogen and argon (the volume ratio of hydrogen to argon is 5:95) to undergo a reduction reaction at a reduction temperature of 800°C and a reduction time of 4 hours. After cooling, a high-performance copper-titanium alloy powder is obtained.

[0074] Depend on Figure 3 It can be seen that the copper-clad titanium powder is well coated and has uniform particle size.

[0075] Depend on Figure 4 It can be seen that the copper-titanium alloy was successfully synthesized.

[0076] Example 4:

[0077] (1) Titanium powder was sequentially added to a 3 mol / L sodium hydroxide solution at room temperature for ultrasonic stirring followed by centrifugal separation, ultrasonic stirring in acetone followed by centrifugal separation, and ultrasonic stirring in anhydrous ethanol followed by centrifugal separation. The ultrasonic stirring process was performed at 200 r / min for 15 min to remove inorganic matter, titanium oxide, and other organic impurities on the surface of the titanium powder to obtain refined titanium powder.

[0078] (2) A copper salt solution with a mass fraction of 16% was prepared using copper formate at room temperature. 30 g of the above-mentioned refined titanium powder was added to 1.5 L of the copper salt solution, and the mixture was mixed uniformly at a stirring speed of 300 r / min for 30 min to obtain a mixture solution.

[0079] (3) Prepare 500 ml of 2 mol / L glucose solution, add it dropwise to the above mixture solution at a rate of 75 ml / min at room temperature, and then react at 80°C for 2 h to allow copper to precipitate on the surface of the titanium powder, plating the titanium powder surface with copper until the titanium powder surface is completely covered with copper, thereby obtaining a mother solution;

[0080] (4) The mother liquid is atomized to form droplets, and the ultrasonic frequency is 1.7 MHz; the droplets are transported to the printing nozzle through the carrier gas, and the carrier gas nitrogen, the constraining gas nitrogen and the droplets together form an aerosol jet. The flow rate of the carrier gas is set to 425 sccm and the flow rate of the constraining gas is set to 125 sccm to control the width and injection speed of the aerosol jet. The aerosol jet is sprayed onto an 80°C substrate, and the printing height is 8 mm. The solvent evaporation rate of the aerosol jet in the air is controlled, and the printing speed is set to 45 mm / s and the number of printing layers is set to 300 layers to control the oxidation process of the aerosol on the substrate, and finally copper-coated titanium powder is obtained on the substrate; nitrogen is used as the carrier gas and the constraining gas;

[0081] (5) The copper-clad titanium powder is annealed in a mixed atmosphere of hydrogen and argon (the volume ratio of hydrogen to argon is 5:95) to undergo a reduction reaction at a reduction temperature of 750°C and a reduction time of 3 hours. After cooling, a high-performance copper-titanium alloy powder is obtained.

[0082] Example 5:

[0083] (1) Titanium powder was sequentially added to a 2.5 mol / L sodium hydroxide solution at room temperature for ultrasonic stirring followed by centrifugal separation, ultrasonic stirring in acetone followed by centrifugal separation, and ultrasonic stirring in anhydrous ethanol followed by centrifugal separation. The ultrasonic stirring process was performed at 200 r / min for 15 min to remove inorganic matter, titanium oxide, and other organic impurities on the surface of the titanium powder to obtain refined titanium powder.

[0084] (2) A copper salt solution with a mass fraction of 25% was prepared using copper nitrate at room temperature. 20 g of the above-mentioned refined titanium powder was added to 4 L of the copper salt solution, and the mixture was mixed evenly at a stirring speed of 900 r / min for 25 min to obtain a mixture solution.

[0085] (3) 1.33 L of a 2 mol / L formalin solution was prepared and added dropwise to the above mixture solution at a rate of 200 ml / min at room temperature, and then reacted at 70°C for 6 h to allow copper to precipitate on the surface of the titanium powder, thereby copper plating the titanium powder surface until the titanium powder surface is completely covered with copper to obtain a mother solution;

[0086] (4) The mother liquid is atomized to form droplets, and the ultrasonic frequency is 1.5 MHz; the droplets are transported to the printing nozzle through the carrier gas, and the carrier gas nitrogen, the constraining gas nitrogen and the droplets together form an aerosol jet. The flow rate of the carrier gas is set to 485 sccm and the flow rate of the constraining gas is set to 150 sccm to control the width and injection speed of the aerosol jet. The aerosol jet is sprayed onto a 200°C substrate, and the printing height is 9 mm. The solvent evaporation rate of the aerosol jet in the air is controlled, and the printing speed is set to 50 mm / s and the number of printing layers is set to 500 layers to control the oxidation process of the aerosol on the substrate, and finally copper-coated titanium powder is obtained on the substrate; nitrogen is used as the carrier gas and the constraining gas;

[0087] (5) The copper-clad titanium powder is annealed in a mixed atmosphere of hydrogen and argon (the volume ratio of hydrogen to argon is 5:95) to undergo a reduction reaction at a reduction temperature of 550°C for 10 hours. After cooling, a high-performance copper-titanium alloy powder is obtained.

[0088]

[0089] Any matters not described in the present invention are applicable to the prior art.

Claims

1. A method for preparing high-performance copper-titanium alloy using aerosol jet printing technology, characterized in that: The method comprises the following steps: Step 1, removing impurities from the surface of the titanium powder to obtain refined titanium powder; Step 2: uniformly mixing the refined titanium powder obtained in step 1 with the copper salt solution to obtain a mixture solution; Step 3, adding a reducing agent solution dropwise to the mixture solution of step 2, and then performing a reduction reaction to precipitate copper on the surface of the titanium powder, thereby copper-plating the surface of the titanium powder until the surface of the titanium powder is completely covered with copper, thereby obtaining a mother liquor; in the reducing agent solution, the reducing agent is ascorbic acid, formalin, hydrazine hydrate, glucose, or hydroxylamine hydrochloride; Step 4: ultrasonically atomizing the mother liquor obtained in step 3 to form droplets at an ultrasonic frequency of 1.5 to 2.5 MHz, and delivering the droplets to an aerosol jet printing device; the droplets are delivered to a printing nozzle via a carrier gas; the carrier gas, the restraining gas, and the droplets together form an aerosol jet, which is ejected from the printing nozzle; the printing height is changed to control the solvent evaporation behavior of the aerosol jet in the air, and a copper-clad titanium powder structure is generated in situ during the flight of the aerosol; the aerosol jet is ejected onto a substrate for aerosol jet printing to obtain copper-clad titanium powder; Step 5: annealing the copper-clad titanium powder obtained in step 4 in a mixed atmosphere of hydrogen and argon to perform a reduction reaction, and then cooling to obtain a high-performance copper-titanium alloy.

2. The method for preparing high-performance copper-titanium alloy using aerosol jet printing technology according to claim 1, characterized in that: Step 1 specifically comprises: adding titanium powder to an alkaline solution for ultrasonic stirring and then centrifuging, adding titanium powder to an organic solvent for ultrasonic stirring and then centrifuging, and adding titanium powder to anhydrous ethanol for ultrasonic stirring and then centrifuging to remove inorganic and organic impurities on the surface of the titanium powder to obtain refined titanium powder.

3. The method for preparing high-performance copper-titanium alloy using aerosol jet printing technology according to claim 2, characterized in that: In step 1, the concentration of the alkali solution is 0.5 mol / L to 3 mol / L; In step 1, the alkali solution is one of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution or sodium phosphate solution; In step 1, the organic solvent is one of acetone, DMF, NMP or DMSO; In step 1, the ultrasonic frequency is 1-2.5 MHz, the stirring speed is 100-5000 r / min, the stirring time is 10-120 min, and the temperature is room temperature.

4. The method for preparing high-performance copper-titanium alloy using aerosol jet printing technology according to claim 1, characterized in that: In step 2, in the copper salt solution, the copper salt is one of copper formate, copper sulfate, copper chloride, copper acetate or copper nitrate, and the solvent is water; In step 2, the mass fraction of the copper salt solution is 10-25 wt %; and the ratio of the mass of the refined titanium powder to the volume of the copper salt solution is 1 g:100-300 ml.

5. The method for preparing high-performance copper-titanium alloy using aerosol jet printing technology according to claim 1, characterized in that: In step 2, the mixing is carried out by stirring; the stirring process is: a rotation speed of 300-1000 r / min, a time of 5-30 min, and a temperature of room temperature.

6. The method for preparing high-performance copper-titanium alloy using aerosol jet printing technology according to claim 1, characterized in that: In step 3, the concentration of the reducing agent solution is 0.5-5 mol / L; the volume ratio of the reducing agent solution to the mixture solution is 1-2:1-5; In step 3, the solvent in the reducing agent solution is water.

7. The method for preparing high-performance copper-titanium alloy using aerosol jet printing technology according to claim 1, characterized in that: In step 3, the dropwise addition rate is 10-200 ml / min; In step 3, the reaction time is 2 to 6 hours, and the reaction temperature is 40 to 80°C.

8. The method for preparing high-performance copper-titanium alloy using aerosol jet printing technology according to claim 1, characterized in that: In step 4, the flow rates of the carrier gas and the confinement gas are changed to control the width and injection velocity of the aerosol jet; the flow rate of the carrier gas is 200-500 sccm, and the flow rate of the confinement gas is 50-150 sccm; In step 4, the printing height is 5~10mm; In step 4, the printing speed, number of printed layers, and substrate temperature are changed to control the oxidation process of the aerosol on the substrate; The printing speed is 5~50mm / s, the number of printing layers is 50~500 layers; the substrate temperature is 40~180℃.

9. The method for preparing high-performance copper-titanium alloy using aerosol jet printing technology according to claim 1, characterized in that: In step 4, nitrogen or argon is used as both the carrier gas and the confinement gas.

10. The method for preparing high-performance copper-titanium alloy using aerosol jet printing technology according to claim 1, characterized in that: In step 5, the reduction reaction temperature is 500-800°C and the time is 3-10 hours; In step 5, the volume ratio of hydrogen to argon is 1-25:75-99, and the sum of the volume ratios of the two is 100%.

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