A nanoparticle-reinforced 1050 aluminum wire suitable for 3D printing and a preparation method thereof

Abstract

The present invention discloses a nanoparticle-reinforced 1050 aluminum wire suitable for 3D printing and a preparation method thereof. The preparation method comprises the following steps: uniformly mixing 1050 aluminum powder, nano-titanium carbide, and an inorganic salt to obtain a precursor powder A; vacuum heating the precursor powder A, and ultrasonically dispersing the powder after melting to obtain a precursor powder B; dissolving the precursor powder B in water and stirring, allowing the suspension to precipitate, and pouring out the upper suspension to obtain a bottom mixed solution C; filtering and drying the bottom mixed solution C to obtain a nanoparticle-reinforced 1050 aluminum composite powder; mixing the composite powder with 1050 aluminum powder and performing powder metallurgy sintering to obtain a nanoparticle-reinforced 1050 aluminum bulk material; heating the bulk material, placing it in an extruder, extruding it, and then annealing and drawing it to obtain a nanoparticle-reinforced 1050 aluminum wire with a desired diameter and nanoparticle content. The material preparation method of the present invention has simple steps, good reproducibility, and can be industrialized for small and medium-scale production.

Description

Technical Field

[0001] The present invention relates to the technical field of aluminum wire preparation, and in particular to a nanoparticle-reinforced 1050 aluminum wire suitable for 3D printing and a preparation method thereof. Background Art

[0002] 1050 aluminum boasts excellent properties such as low density, easy processing, and corrosion resistance. Its products are widely used in construction, electronics, packaging, transportation, and other fields. However, small-batch complex structural products in certain sectors require further improvements in 1050 aluminum's complex formability and mechanical properties. Therefore, the combination of complex-shape 3D printing technology and 1050 aluminum wire can address these performance and complex configuration requirements, which has positive implications for promoting the application of 1050 aluminum in related civilian industries.

[0003] Ceramic particle-reinforced aluminum-matrix composites (AMCs) are a type of aluminum-based composite material obtained by adding dispersed ceramic particles as a reinforcement phase to an aluminum alloy matrix. The reinforcement phase exhibits high strength, high hardness, and a high melting point. Furthermore, because the reinforcement particles are dispersed throughout the metal matrix, their pinning action effectively reduces dislocation motion within the metal matrix, significantly improving the mechanical properties of the material. Traditional reinforcement materials primarily consist of micron or submicron-sized particles. However, recent studies have demonstrated that nanoparticles of equal mass or volume fraction exhibit a more pronounced strengthening effect within the matrix than conventional micron or submicron-sized particles.

[0004] Titanium carbide ceramics, characterized by high temperature resistance, high strength, and high hardness, have found widespread application in industries such as metallurgy, electronics, automotive manufacturing, and aerospace. Nano-titanium carbide ceramic particles inherit these advantages, and a small number of patents exist for nano-titanium carbide ceramic particle-reinforced metal-matrix composites. However, there are no public reports on the preparation of nano-titanium carbide ceramic particle-reinforced lightweight metal wires, particularly those suitable for 3D printing. Summary of the Invention

[0005] The present invention provides a nanoparticle-reinforced 1050 aluminum wire suitable for 3D printing and a preparation method thereof. High-strength nano-titanium carbide ceramic particles are introduced into the 1050 aluminum wire via a molten salt-ultrasonic dispersion-cleaning-filtration-powder sintering-hot extrusion-drawing process. The resulting product can be used to fabricate complex-shaped 1050 aluminum components while also improving the material's mechanical properties. Furthermore, wire materials with varying nano-titanium carbide content can be prepared as required. The method features simple and controllable operating steps, is amenable to scalable production, and offers high batch-to-batch reproducibility.

[0006] The present invention aims to provide a method for preparing nanoparticle-reinforced 1050 aluminum wire suitable for 3D printing, comprising the following steps:

[0007] (1) 1050 aluminum powder, nano-titanium carbide and inorganic salt are uniformly mixed and ball-milled, and sieved to obtain precursor powder A; the volume ratio of the 1050 aluminum powder to the nano-titanium carbide is 1:0.01-0.1, the volume ratio of the sum of the volume of the 1050 aluminum powder and the nano-titanium carbide to the inorganic salt is 5-15:85-95, and the average particle size of the nano-titanium carbide is 40-60 nm;

[0008] (2) The precursor powder A of step (1) is vacuum heated, and after the powder is melted, the melt is subjected to ultrasonic dispersion treatment, and then cooled, and the resulting block solid is crushed to a powder particle size of less than 5 mm to obtain precursor powder B; the vacuum degree during the vacuum heating is ≤6×10 -2 Pa;

[0009] (3) Dissolve the precursor powder B obtained in step (2) in deionized water and stir, then precipitate the dissolved suspension, pour out the upper suspension, and leave the black granular material at the bottom. Repeat this step 3 to 5 times to obtain the bottom mixed solution C.

[0010] (4) The bottom mixed solution C obtained in step (3) is filtered and dried, and the resulting black powder is crushed and sieved in sequence to obtain a nanoparticle-reinforced 1050 aluminum composite powder, wherein the volume fraction of the nanoparticle content in the composite powder is 0.68% to 4.5%;

[0011] (5) mixing the composite powder obtained in step (4) with 1050 aluminum powder and then sintering the mixture by powder metallurgy to obtain the bulk material having nanoparticle-reinforced 1050 aluminum, wherein the volume content of the nanoparticles in the sintered bulk material is between 0.5% and 1.5%;

[0012] (6) heating the bulk material of the nanoparticle-reinforced 1050 aluminum obtained in step (5) and placing it into an extruder, and extruding it to obtain a wire material having nanoparticle-reinforced 1050 aluminum;

[0013] (7) The wire material with nanoparticle-reinforced 1050 aluminum obtained in step (6) is drawn to obtain a nanoparticle-reinforced 1050 aluminum wire material with a desired diameter, wherein the volume percentage of the nanoparticle-reinforced phase in the wire material is between 0.5% and 1.5%.

[0014] The present invention introduces nano-titanium carbide ceramic particles into a 1050 aluminum matrix, and then obtains 1050 aluminum wire reinforced with nano-titanium carbide particles through hot extrusion-drawing. The strengthening effect of the nanoparticles is utilized to improve the mechanical properties and wear resistance of the composite material, which has positive significance for expanding the application of 1050 aluminum composite materials in the industrial field.

[0015] After many experiments, the inventors of the present invention found that if the addition content and particle size of nano-titanium carbide are not properly selected, not only can the preparation of the final wire material not be guaranteed, but the performance may also be weakened; when the particle size of the titanium carbide particles is too large and the particles are too coarse, it is not easy to be introduced into the interior of the 1050 powder during the mixed melting process, and thus it cannot play a good particle reinforcement role; and if the particle size of the nanoparticles is too small, it is difficult to improve the agglomeration defects of the nanoparticles, resulting in difficulty in effectively dispersing the nanoparticles in the wire material after drawing, which is not conducive to improving the material performance. When the relative content of nano-titanium carbide in the precursor powder A is too high, it will cause some nanoparticles to agglomerate, resulting in uneven dispersion and reduced nanoparticle utilization, thereby reducing the particle dispersion effect and increasing costs. In addition, when the volume content of nano-titanium carbide particles in the designed wire material is greater than 1.5%, in the actual drawing state, in addition to causing the deformation performance of the material to deteriorate rapidly, it will also increase the probability of the wire material breaking during the drawing process.

[0016] The method for preparing nanoparticle-reinforced 1050 aluminum wire described in the present invention utilizes a molten salt-ultrasonic dispersion-cleaning-filtration-powder sintering-hot extrusion-drawing process to produce the product. Leveraging the mutual incompatibility of molten 1050 aluminum metal, titanium carbide ceramic particles, and molten salt, the molten salt serves as a dispersion carrier to effectively introduce specific nano-sized solid ceramic particles into the liquid 1050 aluminum. Ultrasonic dispersion then uniformly disperses the reinforcing material particles in the liquid metal. Due to the advantages of titanium carbide, such as high strength, high hardness, high temperature resistance, and a low thermal expansion coefficient, the metal powder material prepared by this method exhibits high hardness, high strength, and high wear resistance. This provides a raw material guarantee and new ideas for expanding the application of high-strength 1050 aluminum composite materials in the industrial field. Furthermore, the nano-titanium carbide particle-reinforced 1050 aluminum-based powder material can also expand the application of 1050 aluminum-based composite materials in additive manufacturing, hot isostatic pressing, and powder metallurgy. The material preparation method described in the present invention has simple operating steps, high reproducibility, safety, and environmental protection, and can be implemented in small-scale industrial production.

[0017] Preferably, the average particle size of the 1050 aluminum powder in step (1) is 10 to 53 μm, and the average particle size of the inorganic salt is 500 to 650 μm.

[0018] After multiple comparative experiments, the inventors found that adding too much nano-titanium carbide can cause the nanoparticles to agglomerate on the surface of the liquid metal, reducing ultrasonic dispersion efficiency and failing to achieve dispersion strengthening. Furthermore, limiting the size of the titanium carbide does not improve these defects. Adding too little fails to achieve the expected performance enhancement. At this ratio, the nano-titanium carbide ceramic particles achieve good dispersion uniformity in the melt after ultrasonic dispersion.

[0019] In addition, inorganic salts serve as carriers for 1050 aluminum and reinforcing particles in molten salt dispersion. If the proportions are inappropriate, this will inevitably lead to problems with material uniformity and production efficiency.

[0020] Preferably, in step (1), the ball milling medium used for ball milling the 1050 aluminum powder, nano-titanium carbide, and inorganic salt is titanium carbide grinding balls, with a ratio of m (titanium carbide grinding balls): m (1050 aluminum powder + nano-titanium carbide + inorganic salt) of 3 to 5:1; the ball milling time is 12 to 24 hours, and the rotation speed is 250 to 300 r / min. Using grinding balls made of the same material as the reinforcing material for ball milling, while limiting the size of the ball milling raw materials and ball milling parameters, can effectively improve ball milling efficiency and avoid the introduction of impurities.

[0021] The inorganic salt includes at least one of potassium chloride and calcium chloride. The two inorganic salts have similar properties and can be mixed in any proportion and effectively used as molten salt and dispersion carrier.

[0022] Preferably, the vacuum heating temperature in step (2) is 800° C. to 830° C. for 5 to 10 minutes, and the ultrasonic dispersion treatment is performed for 2 to 3 minutes at a power of 800 to 1000 W. The object of the ultrasonic dispersion treatment is a molten salt particle mixture, so a specific time and power are required to ensure that the ceramic titanium carbide particles in the melt can be effectively and evenly dispersed into the powder material.

[0023] More preferably, during the ultrasonic dispersion treatment in step (2), the ceramic ultrasonic probe is inserted into the melt for ultrasonic dispersion, and when the ceramic ultrasonic probe is inserted into the melt, the probe tip is located two-thirds below the melt surface.

[0024] Preferably, the precipitation time of the suspension in step (3) is 1 to 2 minutes, and the mass ratio of the deionized water to the precursor powder B is greater than 5:1; and the drying temperature in step (4) is 100°C to 150°C.

[0025] Preferably, in step (5), the composite powder is mixed with 1050 aluminum powder according to the nanoparticle content required by the metal wire, and then sintered, and the powder metallurgy sintering temperature is 560° C. to 595° C.

[0026] Preferably, the heating temperature of the bulk material of the nanoparticle-reinforced 1050 aluminum in step (6) is 400° C. to 430° C., and the extrusion ratio of the bulk material is 80 to 150.

[0027] Preferably, the wire material in step (7) is subjected to stress relief annealing at 300°C to 350°C, and the extruded wire material is drawn at a speed of 10 to 30 m / min. The drawing speed of the present invention, when too low, will result in a decrease in production rate and increased energy costs rather than drawing failure; whereas a higher drawing speed may result in filament breakage.

[0028] Compared to patent CN115889762A (A nano-ceramic particle reinforced 7075 aluminum alloy composite powder, its preparation method, and application), the material has a significant difference in nanoparticle content. To address the stress issue in welded joints, the material disclosed in CN115889762A requires a composite material with a high particle content, with a particle volume fraction greater than 4%. At this volume fraction, the material cannot be drawn and cannot be prepared into a wire suitable for printing. The wire prepared in the present invention has a particle volume fraction of no more than 1.5%, and under these conditions, the material can be drawn into a wire after extrusion.

[0029] Furthermore, compared to pure 1050 aluminum, the addition of nano-ceramic particles generates greater internal stress after extrusion and drawing, making direct drawing or multi-pass continuous drawing impossible and requiring annealing. Therefore, this differs from the continuous drawing of 1050 aluminum wire.

[0030] The present invention also protects the nanoparticle-reinforced 1050 aluminum wire suitable for 3D printing prepared by the above preparation method.

[0031] The present invention also protects the use of the nanoparticle-reinforced 1050 aluminum wire in 3D printing. Compared to existing pure 1050 aluminum wire, the nanoparticle-reinforced 1050 aluminum wire suitable for 3D printing has higher mechanical strength and hardness in printed components. Specifically, compared to existing pure 1050 aluminum wire, the nanoparticle-reinforced 1050 aluminum wire proposed by the present invention has a mechanical strength increase of more than 20% and a hardness increase of more than 10%.

[0032] Compared with the existing technology, the present invention has the following advantages: the preparation method adopts the steps of molten salt-ultrasonic dispersion-cleaning-filtration-powder sintering-hot extrusion-drawing to produce the product. By utilizing the mutual immiscibility of melted 1050 aluminum powder, titanium carbide ceramic particles, and molten salt, the molten salt is used as a dispersion carrier to effectively introduce specific nano-sized solid ceramic particles into the 1050 aluminum material. Ultrasonic dispersion is then used to uniformly disperse the reinforcing material particles in the liquid metal. The resulting nanoparticle-reinforced 1050 aluminum composite powder is metallurgically sintered with 1050 aluminum powder to obtain a nanoparticle-reinforced 1050 aluminum bulk composite material. This is then hot-extruded to obtain the desired nanoparticle-reinforced 1050 aluminum wire material. This is then drawn to obtain a particle-reinforced 1050 aluminum wire with a specified diameter suitable for 3D printing. Because titanium carbide has the advantages of high strength, high hardness, and high temperature resistance, the 1050 aluminum wire prepared by the method has the advantages of high strength, high operating temperature, and good wear resistance, providing a new idea for expanding the application of 1050 aluminum-based composite materials in the field of industrial 3D printing. In addition, the reinforcing phase of the nano-titanium carbide reinforced 1050 aluminum wire, that is, the nano-titanium carbide content, can be adjusted within a certain range to obtain wires with different properties, thereby selecting the appropriate wire according to the component requirements. The material preparation method of the present invention has simple operating steps, high repeatability, safety and environmental protection, and can be realized in industrial small-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is an optical image of the nanoparticle-reinforced 1050 aluminum wire prepared in Example 1 of the present invention;

[0034] Figure 2 This is the SEM image of the interior of the nanoparticle-reinforced 1050 aluminum wire prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0035] The present invention will be described in further detail below with reference to the examples. These examples are intended to illustrate the present invention only and are not intended to limit the scope of the present invention. The experimental methods in the following examples, for which specific conditions are not specified, are generally based on conventional conditions in the art or the conditions recommended by the manufacturer; the raw materials and reagents used, unless otherwise specified, are deemed to be raw materials and reagents that can be obtained through commercial channels such as conventional markets. Any non-substantial changes and substitutions made by those skilled in the art on the basis of the present invention fall within the scope of protection claimed in the present invention.

[0036] Example 1

[0037] An embodiment of a nanoparticle-reinforced 1050 aluminum wire suitable for 3D printing and a preparation method thereof according to the present invention comprises the following steps:

[0038] (1) 1050 aluminum powder, nano-titanium carbide and potassium chloride are placed in a mixing bottle in an argon-protected glove box, titanium carbide grinding balls are added, the bottle is sealed and placed on a mixer for ball milling, and sieved to obtain precursor powder A; the volume ratio of 1050 aluminum powder, nano-titanium carbide and calcium chloride is: v (1050 aluminum powder): v (nano-titanium carbide): v (inorganic salt) = 9.1:0.9:90; the average particle size of nano-titanium carbide is 50nm; the average particle size of 1050 aluminum powder is 40μm, and the average particle size of inorganic salt is 500μm; the mass ratio of titanium carbide grinding balls to 1050 aluminum powder, nano-titanium carbide and inorganic salt is 4:1; the ball milling time is 24h, and the rotation speed is 300r / min;

[0039] (2) The precursor powder A of step (1) was vacuum heated for 10 min. After the powder melted, the obtained melt was inserted into a ceramic ultrasonic probe with the probe tip located two-thirds below the melt surface. Ultrasonic dispersion was performed at a power of 500 W for 3 min. The powder was poured into a ceramic boat for cooling. The obtained block solid was crushed to a powder particle size of <5 mm to obtain precursor powder B. The vacuum degree during vacuum heating was ≤6×10 -2 Pa, heating temperature is 820℃;

[0040] (3) The precursor powder B obtained in step (2) was placed in deionized water and dissolved with stirring, and then the dissolved suspension was precipitated for 2 minutes, and the upper suspension was poured out, leaving the bottom black granular material, and this step was repeated three times to obtain the bottom mixed solution C; the mass ratio of deionized water to precursor powder B was 8:1;

[0041] (4) The bottom mixed solution C obtained in step (3) was filtered and dried at 120° C., and the resulting black powder was crushed and sieved in sequence to obtain a nanoparticle-reinforced 1050 aluminum composite powder. At this time, the volume fraction of the nanoparticle content in the composite powder was 4.5%;

[0042] (5) The composite powder obtained in step (4) is converted to 1050 aluminum powder according to the volume fraction of ceramic particles in the 1050 aluminum wire being 1.5%, and the composite powder and 1050 powder are mixed. After mixing evenly, the mixed powder is subjected to powder metallurgy sintering at 590°C / 30MPa using SPS to obtain a bulk material having nanoparticle-reinforced 1050 aluminum;

[0043] (6) The bulk material of the nanoparticle-reinforced 1050 aluminum obtained in step (5) is heated and kept warm at 410° C. After keeping warm for 20 minutes, the bulk material is placed in an extruder and extruded at an extrusion ratio of 1:90. After extrusion, a wire material having a diameter of 6 mm and nanoparticle-reinforced 1050 aluminum is obtained;

[0044] (7) The nanoparticle-reinforced 1050 aluminum wire obtained in step (6) is first annealed at 300° C. for 1 h. After the wire cools, it is drawn at a speed of 15 m / min. After the drawing is completed, the above steps are repeated until a wire of the desired diameter is obtained. At this time, the volume fraction of the ceramic particles in the 1050 aluminum wire is 1.5%.

[0045] The obtained product was placed under an optical camera for observation, and the results were as follows: Figure 1 As shown, the SEM images are Figure 2 shown.

[0046] Example 2

[0047] The only difference between this embodiment and embodiment 1 is that the steps are:

[0048] (1) 1050 aluminum powder, nano-titanium carbide and calcium chloride are placed in a mixing bottle in an argon-protected glove box, titanium carbide grinding balls are added, the mixture is sealed and placed on a mixer for ball milling, and sieved to obtain precursor powder A; the volume ratio of 1050 aluminum powder, nano-titanium carbide and calcium chloride is: v (1050 aluminum powder): v (nano-titanium carbide): v (inorganic salt) = 9.5:0.5:90; the average particle size of nano-titanium carbide is 40 nm; the average particle size of the 1050 aluminum powder is 40 μm, and the average particle size of the inorganic salt is 500 μm; the mass ratio of titanium carbide grinding balls to the three raw materials of 1050 aluminum powder, nano-titanium carbide and inorganic salt is 4:1; the ball milling time is 24 h, and the rotation speed is 300 r / min;

[0049] (2) The precursor powder A of step (1) was vacuum heated for 10 min. After the powder melted, the obtained melt was inserted into a ceramic ultrasonic probe with the probe tip located two-thirds below the melt surface. Ultrasonic dispersion was performed at 800 W power for 3 min. The powder was poured into a ceramic boat for cooling. The obtained block solid was crushed to a powder particle size of <5 mm to obtain precursor powder B. The vacuum degree during vacuum heating was ≤6×10 -2 Pa; heating temperature is 810℃;

[0050] (3) The precursor powder B obtained in step (2) was placed in deionized water and dissolved with stirring, and then the dissolved suspension was precipitated for 2 minutes, and the upper suspension was poured out, leaving the bottom black granular material, and this step was repeated three times to obtain the bottom mixed solution C; the mass ratio of deionized water to precursor powder B was 8:1;

[0051] (4) The bottom mixed solution C obtained in step (3) was filtered and dried at 120° C., and the resulting black powder was pulverized and sieved in sequence to obtain a nanoparticle-reinforced 1050 aluminum composite powder. At this time, the volume fraction of the nanoparticle content in the composite powder was 2.5%;

[0052] (5) The composite powder obtained in step (4) is converted to 1050 aluminum powder according to the volume fraction of ceramic particles in the 1050 aluminum wire being 0.75%, and the composite powder and 1050 powder are mixed. After mixing evenly, the mixed powder is subjected to powder metallurgy sintering at 560°C / 20MPa using SPS to obtain a bulk material having nanoparticle-reinforced 1050 aluminum;

[0053] (6) heating the bulk material of the nanoparticle-reinforced 1050 aluminum obtained in step (5) at 400° C. for 20 minutes, placing the bulk material into an extruder, and extruding it at an extrusion ratio of 1:150 to obtain a wire material having nanoparticle-reinforced 1050 aluminum;

[0054] (7) The wire material with nanoparticle-reinforced 1050 aluminum obtained in step (6) is first annealed at 350° C. for 1 hour. After the wire is cooled, it is drawn at a speed of 10 m / min. After the drawing is completed, the above steps are repeated until a wire of the desired diameter is obtained. At this time, the volume fraction of the ceramic particles in the 1050 aluminum wire is 0.75%.

[0055] Example 3

[0056] The only difference between this embodiment and embodiment 1 is that the steps are:

[0057] (1) 1050 aluminum powder, nano-titanium carbide and potassium chloride were placed in a mixing bottle in an argon-protected glove box, titanium carbide grinding balls were added, the mixture was sealed and placed on a mixer for ball milling, and sieved to obtain precursor powder A; the volume ratio of 1050 aluminum powder, nano-titanium carbide and potassium chloride was: v(1050 aluminum powder): v(nano-titanium carbide): v(inorganic salt) = 9.5:0.5:90; the average particle size of nano-titanium carbide was 60 nm; the average particle size of 1050 aluminum powder was 40 μm, and the average particle size of inorganic salt was 650 μm; the mass ratio of titanium carbide grinding balls to 1050 aluminum powder, nano-titanium carbide and inorganic salt was 4:1; the ball milling time was 24 h, and the rotation speed was 300 r / min;

[0058] (2) The precursor powder A of step (1) was vacuum heated for 10 min. After the powder melted, the obtained melt was inserted into a ceramic ultrasonic probe with the probe tip located two-thirds below the melt surface. Ultrasonic dispersion was performed at 800 W power for 3 min. The powder was poured into a ceramic boat for cooling. The obtained block solid was crushed to a powder particle size of <5 mm to obtain precursor powder B. The vacuum degree during vacuum heating was ≤6×10 -2 Pa; heating temperature is 820℃;

[0059] (3) The precursor powder B obtained in step (2) was placed in deionized water and dissolved with stirring, and then the dissolved suspension was precipitated for 2 minutes, and the upper suspension was poured out, leaving the bottom black granular material, and this step was repeated three times to obtain the bottom mixed solution C; the mass ratio of deionized water to precursor powder B was 8:1;

[0060] (4) The bottom mixed solution C obtained in step (3) was filtered and dried at 120° C., and the resulting black powder was pulverized and sieved in sequence to obtain a nanoparticle-reinforced 1050 aluminum powder composite material. At this time, the volume fraction of the nanoparticle content in the composite powder was 2.5%;

[0061] (5) The composite powder obtained in step (4) is converted to 1050 aluminum powder according to the volume fraction of ceramic particles in the 1050 aluminum wire being 0.5%, and the composite powder and 1050 powder are mixed. After mixing evenly, the mixed powder is subjected to powder metallurgy sintering at 560°C / 20MPa using SPS to obtain a bulk material having nanoparticle-reinforced 1050 aluminum;

[0062] (6) The bulk material of the nanoparticle-reinforced 1050 aluminum obtained in step (5) is heated and kept warm at 430° C. After keeping warm for 20 minutes, the bulk material is placed in an extruder and extruded at an extrusion ratio of 1:120 to obtain a wire material having nanoparticle-reinforced 1050 aluminum;

[0063] (7) The nanoparticle-reinforced 1050 aluminum wire obtained in step (6) is first annealed at 320° C. for 1 h. After the wire is cooled, it is drawn at a speed of 20 m / min. After the drawing is completed, the above steps are repeated until a wire of the desired diameter is obtained. At this time, the volume fraction of the ceramic particles in the 1050 aluminum wire is 0.5%.

[0064] Example 4

[0065] The only difference between this embodiment and embodiment 1 is that the steps are:

[0066] (1) 1050 aluminum powder, nano-titanium carbide, potassium chloride and calcium chloride are placed in a mixing bottle in an argon-protected glove box, titanium carbide grinding balls are added, the mixture is sealed and placed on a mixer for ball milling, and sieved to obtain precursor powder A; the volume ratio of 1050 aluminum powder, nano-titanium carbide, potassium chloride and calcium chloride is: v(1050 aluminum powder):v(nano-titanium carbide):v(potassium chloride):v(calcium chloride)=9.2:0.8:10:80; the average particle size of nano-titanium carbide is 50nm; the average particle size of 1050 aluminum powder is 26μm, the average particle size of potassium chloride is 500μm; the average particle size of calcium chloride is 650μm; the mass ratio of titanium carbide grinding balls to 1050 aluminum powder, nano-titanium carbide and inorganic salt is 4:1; the ball milling time is 24h, and the rotation speed is 300r / min;

[0067] (2) The precursor powder A of step (1) was vacuum heated for 10 min. After the powder melted, the obtained melt was inserted into a ceramic ultrasonic probe with the probe tip located two-thirds below the melt surface. Ultrasonic dispersion was performed at 800 W power for 3 min. The powder was poured into a ceramic boat for cooling. The obtained block solid was crushed to a powder particle size of <5 mm to obtain precursor powder B. The vacuum degree during vacuum heating was ≤6×10 -2 Pa; heating temperature is 830℃;

[0068] (3) The precursor powder B obtained in step (2) was placed in deionized water and dissolved with stirring, and then the dissolved suspension was precipitated for 2 minutes, and the upper suspension was poured out, leaving the bottom black granular material, and this step was repeated three times to obtain the bottom mixed solution C; the mass ratio of deionized water to precursor powder B was 8:1;

[0069] (4) The bottom mixed solution C obtained in step (3) was filtered and dried at 120° C., and the resulting black powder was pulverized and sieved in sequence to obtain a nanoparticle-reinforced 1050 aluminum composite powder. At this time, the volume fraction of the nanoparticles in the composite powder was 4.2%;

[0070] (5) The composite powder obtained in step (4) is converted to 1050 aluminum powder according to the volume fraction of ceramic particles in the 1050 aluminum wire being 1.5%, and the composite powder and 1050 powder are mixed. After mixing evenly, the mixed powder is subjected to powder metallurgy sintering at 580°C / 30MPa using SPS to obtain a bulk material having nanoparticle-reinforced 1050 aluminum;

[0071] (6) The bulk material of the nanoparticle-reinforced 1050 aluminum obtained in step (5) is heated and kept warm at 420° C. After keeping warm for 20 minutes, the bulk material is placed in an extruder and extruded at an extrusion ratio of 1:80 to obtain a wire material having nanoparticle-reinforced 1050 aluminum;

[0072] (7) The wire material with nanoparticle-reinforced 1050 aluminum obtained in step (6) is first annealed at 320° C. for 1 hour. After the wire is cooled, it is drawn at a speed of 10 m / min. After the drawing is completed, the above steps are repeated until a wire of the desired diameter is obtained. At this time, the volume fraction of the ceramic particles in the 1050 aluminum wire is 1.5%.

[0073] Example 5

[0074] The only difference between this embodiment and embodiment 1 is that the steps are:

[0075] (1) 1050 aluminum powder, nano-titanium carbide, potassium chloride and calcium chloride are placed in a mixing bottle in an argon-protected glove box, titanium carbide grinding balls are added, the mixture is sealed and placed on a mixer for ball milling, and sieved to obtain precursor powder A; the volume ratio of the 1050 aluminum powder, nano-titanium carbide, potassium chloride and calcium chloride is: v(1050 aluminum powder):v(nano-titanium carbide):v(potassium chloride):v(calcium chloride)=4.6:0.4:45:50; the average particle size of nano-titanium carbide is 50 nm; the average particle size of the 1050 aluminum powder is 26 μm, the average particle size of potassium chloride is 500 μm; the average particle size of calcium chloride is 500 μm; the mass ratio of titanium carbide grinding balls to the three raw materials of 1050 aluminum powder, nano-titanium carbide and inorganic salt is 4:1; the ball milling time is 24 h, and the rotation speed is 300 r / min;

[0076] (2) The precursor powder A described in step (1) was vacuum heated for 10 min. After the powder melted, the obtained melt was inserted into a ceramic ultrasonic probe with the probe tip located two-thirds below the melt surface. Ultrasonic dispersion was performed at a power of 600 W for 3 min. The powder was poured into a ceramic boat for cooling. The obtained block solid was crushed to a powder particle size of <5 mm to obtain precursor powder B. The vacuum degree during vacuum heating was ≤6×10 -2 Pa; heating temperature is 810℃;

[0077] (3) The precursor powder B obtained in step (2) was placed in deionized water and dissolved with stirring, and then the dissolved suspension was precipitated for 2 minutes, and the upper suspension was poured out, leaving the bottom black granular material, and this step was repeated three times to obtain the bottom mixed solution C; the mass ratio of the deionized water to the precursor powder B was 10:1;

[0078] (4) The bottom mixed solution C obtained in step (3) was filtered and dried at 120° C., and the resulting black powder was crushed and sieved in sequence to obtain the nanoparticle-reinforced 1050 aluminum powder composite material. At this time, the volume fraction of the nanoparticle content in the composite powder was 4.0%;

[0079] (5) The composite powder obtained in step (4) is converted to 1050 aluminum powder according to the volume fraction of ceramic particles in the 1050 aluminum wire being 0.75%, and the composite powder and 1050 powder are mixed. After mixing evenly, the mixed powder is subjected to powder metallurgy sintering at 580° C. / 30 MPa using SPS to obtain the bulk material having nanoparticle-reinforced 1050 aluminum;

[0080] (6) heating the bulk material of the nanoparticle-reinforced 1050 aluminum obtained in step (5) at 430° C. for 20 minutes, placing the bulk material into an extruder, and extruding it at an extrusion ratio of 1:100 to obtain a wire material having nanoparticle-reinforced 1050 aluminum;

[0081] (7) The nanoparticle-reinforced 1050 aluminum wire obtained in step (6) is first annealed at 310° C. for 1 h. After the wire is cooled, it is drawn at a speed of 15 m / min. After the drawing is completed, the above steps are repeated until a wire of the desired diameter is obtained. At this time, the volume fraction of the ceramic particles in the 1050 aluminum wire is 0.75%.

[0082] Example 6

[0083] The only difference between this embodiment and embodiment 1 is that the steps are:

[0084] (1) 1050 aluminum powder, nano-titanium carbide and potassium chloride are placed in a mixing bottle in an argon-protected glove box, titanium carbide grinding balls are added, the mixture is sealed and placed on a mixer for ball milling, and sieved to obtain precursor powder A; the volume ratio of 1050 aluminum powder, nano-titanium carbide and potassium chloride is: v (1050 aluminum powder): v (nano-titanium carbide): v (inorganic salt) = 14.4:0.6:85; the average particle size of nano-titanium carbide is 60 nm; the average particle size of 1050 aluminum powder is 53 μm, and the average particle size of inorganic salt is 650 μm; the mass ratio of titanium carbide grinding balls to 1050 aluminum powder, nano-titanium carbide and inorganic salt is 4:1; the ball milling time is 24 h, and the rotation speed is 300 r / min;

[0085] (2) The precursor powder A described in step (1) was vacuum heated for 10 min. After the powder melted, the obtained melt was inserted into a ceramic ultrasonic probe with the probe tip located two-thirds below the melt surface. Ultrasonic dispersion was performed at a power of 700 W for 3 min. The powder was poured into a ceramic boat for cooling. The obtained block solid was crushed to a powder particle size of <5 mm to obtain precursor powder B. The vacuum degree during vacuum heating was ≤6×10 -2 Pa; heating temperature is 810℃;

[0086] (3) The precursor powder B obtained in step (2) was placed in deionized water and dissolved with stirring, and then the dissolved suspension was precipitated for 2 minutes, and the upper suspension was poured out, leaving the bottom black granular material, and this step was repeated three times to obtain the bottom mixed solution C; the mass ratio of deionized water to precursor powder B was 6:1;

[0087] (4) The bottom mixed solution C obtained in step (3) was filtered and dried at 120° C., and the resulting black powder was pulverized and sieved in sequence to obtain a nanoparticle-reinforced 1050 aluminum powder composite material. At this time, the volume fraction of the nanoparticles in the composite powder was 2.1%;

[0088] (5) The composite powder obtained in step (4) is converted to 1050 aluminum powder according to the volume fraction of ceramic particles in the 1050 aluminum wire being 0.8%, and the composite powder and 1050 powder are mixed. After mixing evenly, the mixed powder is subjected to powder metallurgy sintering at 580°C / 30MPa using SPS to obtain a bulk material having nanoparticle-reinforced 1050 aluminum;

[0089] (6) heating the bulk material of the nanoparticle-reinforced 1050 aluminum obtained in step (5) at 400° C. for 15 minutes, placing the bulk material into an extruder, and extruding it at an extrusion ratio of 1:90 to obtain a wire material having nanoparticle-reinforced 1050 aluminum;

[0090] (7) The wire material with nanoparticle-reinforced 1050 aluminum obtained in step (6) is first annealed at 340° C. for 1 hour. After the wire is cooled, it is drawn at a speed of 30 m / min. After the drawing is completed, the above steps are repeated until a wire of the desired diameter is obtained. At this time, the volume fraction of the ceramic particles in the 1050 aluminum wire is 0.8%.

[0091] Example 7

[0092] The only difference between this embodiment and embodiment 1 is that the steps are:

[0093] (1) 1050 aluminum powder, nano-titanium carbide, calcium chloride and potassium chloride are placed in a mixing bottle in an argon-protected glove box, titanium carbide grinding balls are added, the mixture is sealed and placed on a mixer for ball milling, and sieved to obtain precursor powder A; the volume ratio of 1050 aluminum powder, nano-titanium carbide, potassium chloride and calcium chloride is: v(1050 aluminum powder):v(nano-titanium carbide):v(potassium chloride):v(calcium chloride)=9.8:0.2:80:10; the average particle size of nano-titanium carbide is 50nm; the average particle size of 1050 aluminum powder is 26μm, the average particle size of potassium chloride is 500μm; the average particle size of calcium chloride is 600μm; the mass ratio of titanium carbide grinding balls to 1050 aluminum powder, nano-titanium carbide and inorganic salt is 4:1; the ball milling time is 24h, and the rotation speed is 300r / min;

[0094] (2) The precursor powder A of step (1) was vacuum heated for 10 min. After the powder melted, the melt was inserted into a ceramic ultrasonic probe and ultrasonically dispersed at 800 W for 3 min. The melt was poured into a ceramic boat for cooling. The resulting block solid was crushed to a powder particle size of <5 mm to obtain precursor powder B. The vacuum degree during vacuum heating was ≤6×10 -2 Pa; heating temperature is 820℃;

[0095] (3) The precursor powder B obtained in step (2) was placed in deionized water and dissolved with stirring, and then the dissolved suspension was precipitated for 3 minutes, and the upper suspension was poured out, leaving the bottom black granular material, and this step was repeated 5 times to obtain the bottom mixed solution C; the mass ratio of deionized water to precursor powder B was 8:1;

[0096] (4) The bottom mixed solution C obtained in step (3) was filtered and dried at 150° C., and the resulting black powder was pulverized and sieved in sequence to obtain a nanoparticle-reinforced 1050 aluminum powder composite material. At this time, the volume fraction of the nanoparticle content in the composite powder was 0.91%;

[0097] (5) The composite powder obtained in step (4) is converted to 1050 aluminum powder according to the volume fraction of ceramic particles in the 1050 aluminum wire being 0.5%, and the composite powder and 1050 powder are mixed. After mixing evenly, the mixed powder is subjected to powder metallurgy sintering at 575°C / 30MPa using SPS to obtain a bulk material having nanoparticle-reinforced 1050 aluminum;

[0098] (6) The bulk material of the nanoparticle-reinforced 1050 aluminum obtained in step (5) is heated and kept warm at 410° C. After keeping warm for 20 minutes, the bulk material is placed in an extruder and extruded at an extrusion ratio of 1:100 to obtain a wire material having nanoparticle-reinforced 1050 aluminum;

[0099] (7) The wire material with nanoparticle-reinforced 1050 aluminum obtained in step (6) is first annealed at 300° C. for 1 hour. After the wire is cooled, it is drawn at a speed of 20 m / min. After the drawing is completed, the above steps are repeated until a wire of the desired diameter is obtained. At this time, the volume fraction of the ceramic particles in the 1050 aluminum wire is 0.5%.

[0100] Comparative Example 1

[0101] The only difference between this comparative example and Example 1 is that the step (1) is:

[0102] 1050 aluminum powder, nano-titanium carbide and potassium chloride were placed in a mixing bottle in an argon-protected glove box, titanium carbide grinding balls were added, the mixture was sealed and placed on a mixer for ball milling, and sieved to obtain precursor powder A; the volume ratio of 1050 aluminum powder, nano-titanium carbide and potassium chloride was: v(1050 aluminum powder):v(nano-titanium carbide):v(inorganic salt)=15:5:80; the average particle size of nano-titanium carbide was 50 nm; the average particle size of 1050 aluminum powder was 26 μm, and the average particle size of inorganic salt was 500 μm; the mass ratio of titanium carbide grinding balls to 1050 aluminum powder, nano-titanium carbide and inorganic salt was 4:1; the ball milling time was 24 h, and the rotation speed was 300 r / min;

[0103] (6) The bulk material of the nanoparticle-reinforced 1050 aluminum obtained in step (5) is heated and kept warm at 480° C. After keeping warm for 20 minutes, the bulk material is placed in an extruder and extruded at an extrusion ratio of 1:200. After extrusion, a wire material having nanoparticle-reinforced 1050 aluminum is obtained.

[0104] Comparative Example 2

[0105] The difference between this comparative example and Example 1 is that the steps are as follows:

[0106] (1) 1050 aluminum powder, nano-titanium carbide and potassium chloride are placed in a mixing bottle in an argon-protected glove box, titanium carbide grinding balls are added, the mixture is sealed and placed on a mixer for ball milling, and sieved to obtain precursor powder A; the volume ratio of 1050 aluminum powder, nano-titanium carbide and calcium chloride is: v (1050 aluminum powder): v (nano-titanium carbide): v (inorganic salt) = 8:2:90; the average particle size of nano-titanium carbide is 50 nm; the average particle size of 1050 aluminum powder is 26 μm, and the average particle size of inorganic salt is 500 μm; the mass ratio of titanium carbide grinding balls to 1050 aluminum powder, nano-titanium carbide and inorganic salt is 4:1; the ball milling time is 24 h, and the rotation speed is 300 r / min;

[0107] (2) The precursor powder A of step (1) was vacuum heated for 10 min. After the powder melted, the melt was stirred for 3 min, poured into a ceramic boat and cooled. The resulting block solid was crushed to a powder particle size of <5 mm to obtain precursor powder B. The vacuum degree during vacuum heating was ≤6×10 -2 Pa; heating temperature is 800℃;

[0108] (3) The precursor powder B obtained in step (2) was placed in deionized water and dissolved with stirring, and then the dissolved suspension was precipitated for 2 minutes, and the upper suspension was poured out, leaving the bottom black granular material, and this step was repeated three times to obtain the bottom mixed solution C; the mass ratio of deionized water to precursor powder B was greater than 5:1;

[0109] (4) The bottom mixed solution C obtained in step (3) was filtered and dried at 120° C., and the obtained black powder was crushed and sieved in sequence to obtain a 1050 aluminum powder composite material;

[0110] (5) The composite powder obtained in step (4) is mixed with 1050 aluminum powder according to a volume fraction of ceramic particles of 1%, and after mixing evenly, the mixed powder is subjected to powder metallurgy sintering at 575°C / 20MPa using SPS to obtain a bulk material having nanoparticle-reinforced 1050 aluminum;

[0111] (6) heating the bulk material of the nanoparticle-reinforced 1050 aluminum obtained in step (5) at 500° C. for 15 minutes, placing the bulk material into an extruder, and extruding it at an extrusion ratio of 1:120 to obtain a wire material having nanoparticle-reinforced 1050 aluminum;

[0112] (7) The wire material with nanoparticle-reinforced 1050 aluminum obtained in step (6) is first annealed at 200° C. for 1 hour. After the wire is cooled, it is drawn at a speed of 40 m / min. After the drawing is completed, the above steps are repeated until a wire of the desired diameter is obtained.

[0113] Effect Example 1

[0114] To verify the effect of the nanoparticle content on the particle dispersion performance of the nanoparticle-reinforced 1050 aluminum wire of the present invention during the mixing process, microstructural observations were performed on the wires prepared in Example 1 and Comparative Example 1. It was found that when the nanoparticle content was too high during the mixing process, it was difficult to effectively disperse the nanoparticles in the matrix, and the particle dispersion could not be achieved even after multiple drawing cycles.

[0115] Effect Example 2

[0116] In order to verify the drawing effect of the nanoparticle-reinforced 1050 aluminum wire of the present invention during the drawing process, the wires prepared in Example 1 and Comparative Example 2 were drawn and observed. It was found that when the drawing speed was too fast and the annealing temperature was not enough, even if the annealing after drawing would reduce the internal stress, it would still cause the wire to break easily during the drawing process, especially in small diameter materials (less than 1.5 mm in diameter).

[0117] For those skilled in the art, various other corresponding compositions can be made according to the technical solutions and concepts described above, that is, the generated phase is mainly 1050 aluminum-based composite material reinforced with nano-titanium carbide particles (TiC np / 1050Al), including but not limited to 1050, 1060, 1070, and 1080 series pure aluminum materials. During this process, changes in raw material particle size, raw material ratio, dispersion process, ultrasonic power, drying process, sintering process, extrusion process, and drawing process are all within the scope of protection of the claims of the present invention.

[0118] The above are merely preferred embodiments of the present invention. It should be noted that the above preferred embodiments should not be construed as limiting the present invention, and the scope of protection of the present invention should be determined by the scope defined in the claims. Persons skilled in the art will appreciate that improvements and modifications may be made without departing from the spirit and scope of the present invention, and such improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing nanoparticle-reinforced 1050 aluminum wire suitable for 3D printing, characterized in that: The following steps are involved: (1) 1050 aluminum powder, nano-titanium carbide and inorganic salt are uniformly mixed and ball-milled, and sieved to obtain precursor powder A; the volume ratio of the 1050 aluminum powder to the nano-titanium carbide is 1:0.01-0.1, the volume ratio of the sum of the volume of the 1050 aluminum powder and the nano-titanium carbide to the inorganic salt is 5-15:85-95, and the average particle size of the nano-titanium carbide is 40-60 nm; (2) The precursor powder A of step (1) is vacuum heated, and after the powder is melted, the melt is subjected to ultrasonic dispersion treatment, and then cooled, and the obtained block solid is crushed to a powder particle size of less than 5 mm to obtain precursor powder B; the vacuum degree during the vacuum heating is ≤6×10 -2 Pa; (3) The precursor powder B obtained in step (2) is placed in deionized water and dissolved and stirred, and then the dissolved suspension is precipitated, and the upper suspension is poured out, leaving the bottom black granular material, and this step is repeated 3 to 5 times to obtain the bottom mixed solution C; (4) The bottom mixed solution C obtained in step (3) is filtered and dried, and the obtained black powder is crushed and sieved in sequence to obtain a nanoparticle-reinforced 1050 aluminum composite powder. At this time, the volume fraction of the nanoparticle content in the composite powder is 0.68% to 4.5%; (5) mixing the composite powder obtained in step (4) with 1050 aluminum powder and then performing powder metallurgy sintering to obtain a bulk material having nanoparticle-reinforced 1050 aluminum, wherein the volume content of the nanoparticles in the sintered bulk material is between 0.5% and 1.5%; (6) The bulk material of the nanoparticle-reinforced 1050 aluminum obtained in step (5) is heated and placed into an extruder, and a wire material having nanoparticle-reinforced 1050 aluminum is obtained after extrusion, wherein the heating temperature of the bulk material of the nanoparticle-reinforced 1050 aluminum is 400° C. to 430° C., and the extrusion ratio of the bulk material is 80 to 150; (7) The wire material with nanoparticle-reinforced 1050 aluminum obtained in step (6) is drawn to obtain a nanoparticle-reinforced 1050 aluminum wire material with a desired diameter. The volume percentage of the nanoparticle-reinforced phase in the wire material is between 0.5% and 1.5%. The wire material needs to be subjected to stress relief annealing treatment at 300° C. to 350° C. During the drawing process, the drawing speed of the extruded wire material is 10 to 30 m / min.

2. The preparation method according to claim 1, characterized in that The average particle size of the 1050 aluminum powder in step (1) is 10-53 μm, the average particle size of the inorganic salt is 500-650 μm, and the ball milling medium used in the ball milling treatment of the 1050 aluminum powder, nano-titanium carbide and inorganic salt is titanium carbide grinding ball, m (titanium carbide grinding ball): m (1050 aluminum powder + nano-titanium carbide + inorganic salt) = 3-5:1; the ball milling treatment time is 12-24 h, and the rotation speed is 250-300 r / min.

3. The preparation method according to claim 1 or 2, characterized in that The vacuum heating in step (2) is performed at a temperature of 800°C to 830°C for 5 to 10 minutes; the ultrasonic dispersion treatment is performed at a power of 800 to 1000 W for 2 to 3 minutes.

4. The preparation method according to claim 1 or 2, characterized in that The precipitation time of the suspension in step (3) is 1 to 2 minutes; the drying temperature in step (4) is 100°C to 150°C.

5. The preparation method according to claim 1 or 2, characterized in that In step (5), the composite powder is mixed with 1050 aluminum powder according to the nanoparticle content required by the metal wire, and then sintered. The powder metallurgy sintering temperature is 560° C. to 595° C.

6. Nanoparticle-reinforced 1050 aluminum wire suitable for 3D printing, prepared by the preparation method according to claim 1 or 2.

7. Use of the nanoparticle-reinforced 1050 aluminum wire according to claim 6 in 3D printing.

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