Method for preparing metal alloy, product, and use

Abstract

A method for preparing a metal alloy. The method comprises: mixing a base metal powder, a metal crosslinking agent, and a metal crosslinking initiator, and subjecting the mixture to a metal polymerization reaction to obtain a metal alloy; the metal crosslinking agent is a liquid metal selected from one or more of gallium, indium, tin, zinc, bismuth, and lead, or one or more of multi-element alloys composed of gallium, indium, tin, zinc, and bismuth; and the metal crosslinking initiator is a basic salt or a base. The preparation method is carried out at room temperature, and the prepared metal alloy exhibits excellent mechanical properties, and an excellent elastic modulus and hardness. The present invention further relates to a metal alloy and a processing method for the structural parts thereof.

Description

A method for preparing a metal alloy, the product and its application Technical Field

[0001] This invention relates to the field of metal materials technology, and in particular to a method for preparing a metal alloy, a product thereof, and its application. Background Technology

[0002] The formation of metal alloys involves the interdiffusion of multiple metal atoms in a solid or liquid state at high temperatures, further forming new crystal structures. 3D printing technology enables the rapid prototyping of metal alloys, primarily through selective laser melting (SLM) and binder jet additive manufacturing methods. The former utilizes high-density energy radiation to melt the metal, while the latter completes the melting process through debinding and subsequent remelting in a tube furnace. However, the preparation of almost all metal alloys requires high-temperature and high-energy conditions, typically exceeding 1000°C. The differences in melting points of different metals during the fusion process increase the preparation cost and technical difficulty. This mainly includes the handling requirements of different metal materials during phase transformation and crystallization, requiring precise control of temperature and heating processes to ensure the alloy achieves the required uniformity and high strength. Therefore, achieving the melting and remelting of alloys at room temperature using mild chemical methods in the field of metal materials is a significant technical challenge. Summary of the Invention

[0003] This invention aims to solve the technical challenge of preparing metal polymers at room temperature. To this end, this invention proposes a metal polymerization method that is simple to operate, and the resulting metal polymer exhibits good mechanical properties, showing broad market application prospects in the industrial field.

[0004] This invention discloses a method for preparing high-strength alloys, defined as a metal polymerization reaction. During the metal polymerization reaction, the eutectic phase of the base metal powder and the metal crosslinking agent undergoes polymerization under the action of a metal crosslinking initiator, forming a new alloy phase. Through the metal polymerization reaction, the alloy transforms into a solid alloy at room temperature, forming a novel alloy structure. This polymerization process utilizes the chemical kinetics and thermodynamic characteristics of the reaction to control the arrangement of metal atoms in the crystal, thereby regulating the mechanical properties of the alloy. This invention pioneers a new method for alloy preparation through room-temperature polymerization, which not only improves the strength and hardness of the prepared alloy but also enhances its corrosion resistance and thermal stability.

[0005] The technical solution adopted in this invention is as follows:

[0006] A method for preparing a metal alloy includes: mixing a base metal powder, a metal crosslinking agent, and a metal crosslinking initiator, and carrying out a metal polymerization reaction to obtain the metal alloy; wherein the metal crosslinking agent is a liquid metal selected from one or more of gallium, indium, tin, zinc, bismuth, and lead, or one or more of a multi-element alloy composed of gallium, indium, tin, zinc, bismuth, and lead; and wherein the metal crosslinking initiator is a basic salt or an alkali.

[0007] Furthermore, the metal crosslinking initiator is a hydroxide-soluble basic salt or base with a pH value greater than or equal to 7.5.

[0008] Furthermore, the base metal powder is one or more of the following metals or metal alloys: Mg, magnesium-aluminum alloy, Ti, titanium-aluminum alloy, V, vanadium-aluminum alloy, Cr, chromium-aluminum alloy, Fe, iron-aluminum alloy, Co, cobalt-aluminum alloy, Ni, nickel-aluminum alloy, Cu, copper-aluminum alloy, Zn, zinc-aluminum alloy, Ag, Sn, Pt, and Au.

[0009] According to some embodiments of the present invention, the particulate metal is a magnesium-aluminum alloy, titanium, vanadium-aluminum alloy, chromium powder and chromium-aluminum alloy, iron-aluminum alloy, cobalt-aluminum alloy, nickel-aluminum alloy, copper-aluminum alloy, zinc-aluminum alloy, silver, tin, and gold powder, etc. More preferably, it is one or more of the aluminum alloys corresponding to Fe, Co, Ni, Zn, Cu, Ti, V, and Cr (i.e., one or more of iron-aluminum alloy, cobalt-aluminum alloy, nickel-aluminum alloy, copper-aluminum alloy, zinc-aluminum alloy, titanium-aluminum alloy, vanadium-aluminum alloy, and chromium-aluminum alloy), which can be denoted as MxAly, wherein the mass percentage content of aluminum atoms is 5%-40%; more preferably 10%-35%; even more preferably 15%-30%; specifically preferably 20%-30%. Using aluminum alloys, during the polymerization process, Al in the aluminum alloy slowly dissolves in the system, thus ensuring a slow and stable polymerization reaction, resulting in a more complete reaction, further optimization of the alloy structure, and better mechanical properties.

[0010] Furthermore, the liquid metal is one or more of gallium-indium liquid metal, gallium-indium-zinc liquid metal, gallium-indium-tin liquid metal, gallium-indium-tin-bismuth liquid metal, and gallium-indium-tin-zinc liquid metal. Taking gallium-indium liquid metal as an example, eutectic gallium-indium alloy, as a liquid metal, is a typical example of a covalent metal, in which gallium atoms exhibit covalent bonds at 12°C. Similar to the reactions of covalent organic frameworks and metal-organic frameworks, polymerization occurs when eutectic gallium-indium and aluminum-doped transition alloys are mixed.

[0011] Furthermore, the metal crosslinking initiator is an aqueous solution of one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia; preferably sodium hydroxide.

[0012] According to some embodiments of the present invention, the metal crosslinking initiator is a basic salt, and the cation is a metal ion (or NH4+). 4+ ) salt.

[0013] Further, the mass ratio of the metal crosslinking agent to the base metal powder is 100:(30-100); preferably, the mass ratio of the metal crosslinking agent to the base metal powder is 100:(30-90); even more preferably, the mass ratio of the metal crosslinking agent to the base metal powder is 100:(30-80); and even further, the mass ratio of the metal crosslinking agent to the base metal powder is 100:(30-65).

[0014] Furthermore, the mass ratio of the metal crosslinking initiator to the metal crosslinking agent is 1:(0.01-0.1); more preferably 1:(0.01-0.05).

[0015] Furthermore, the temperature for metal polymerization reactions is 11–30°C.

[0016] Furthermore, the metal polymerization reaction time ranges from 1 s to 1200 s.

[0017] Furthermore, the particle size of the base metal powder is 15-53 μm.

[0018] A metal alloy comprising: obtained by the method described in any one of the preceding embodiments.

[0019] A metal alloy structure is obtained by mixing the base metal powder, metal crosslinking agent, and metal crosslinking initiator described in any one of the above-mentioned methods, and then casting the mixture into a corresponding mold to obtain the metal polymer part; or by mixing the base metal powder, metal crosslinking agent, and metal crosslinking initiator using an extrusion printer to obtain the metal alloy structure; or by directly coating the base metal powder, metal crosslinking agent, and metal crosslinking initiator onto the target location for in-situ polymerization to form the metal alloy structure.

[0020] The above methods can be used to process alloy parts with various structures. For alloy parts with three-dimensional structures, the three-dimensional structure can be designed first using 3D software, and then the mold structure or 3D printing path can be designed based on the 3D graphic file. The mold or 3D printing device can then be used for processing. When processing alloy structures using 3D printing, a dual-nozzle printing method is generally used, with one nozzle containing base metal powder + metal crosslinking agent and the other containing metal crosslinking initiator. Alternatively, an "adhesive coating" method can be used to process alloy structures, where the base metal powder + metal crosslinking agent and metal crosslinking initiator are extruded through different dispensing extruders at the target location, forming a specific structure at that location, such as for the remanufacturing of high-frequency electromagnetic shielding metal materials.

[0021] As a preferred embodiment, the "basic metal powder" in this invention is copper-aluminum alloy powder.

[0022] As a preferred embodiment, the "metal crosslinking agent" in this invention is a gallium-indium metal alloy.

[0023] According to some embodiments of the present invention, the new alloy after metal polymerization has a mass of over 90%.

[0024] Taking mold processing as an example, the processing procedure is explained as follows:

[0025] This invention provides a metal polymerization method, comprising the following steps:

[0026] (1) Making molds for metal polymerization; the mold structure is generally determined based on the structure of the metal structural parts;

[0027] (2) The raw materials include basic metal powder, metal crosslinking agent and metal crosslinking initiator. The three are fused in a certain proportion to form a raw material liquid for metal polymerization reaction at room temperature.

[0028] (3) The mixed raw material liquid is filled into the mold to form a polymer model in 10-20 minutes;

[0029] (4) In order to obtain an alloy material with excellent mechanical properties, pressure is applied to the original model of the polymer and static pressure is applied for 24 hours (or other times, such as 5 to 40 hours, depending on the material) to obtain a new alloy part.

[0030] The metals in the resulting alloy are linked by metallic bonds.

[0031] Taking the base metal powder as an example of copper-aluminum alloy, the above preparation method is completed by a mold and copper-aluminum metal filled in the mold to obtain a new alloy material with a crystal structure.

[0032] According to some embodiments of the present invention, in step (1), the base metal powder and the metal crosslinking agent are formed by cold pressing, with a pressure of 50-100 MPa and a holding time of 10-30 hours (24 hours). The operation process is simple and can prepare large-scale alloys with complex structures.

[0033] According to some embodiments of the present invention, the process of the treatment in step (4) is as follows: the polymerization reaction is carried out at room temperature and the mixture is initially cured, and then a new alloy is formed under pressure.

[0034] This invention provides a novel alloy obtained by metal polymerization, prepared according to the metal polymerization method described above.

[0035] According to some embodiments of the present invention, during the metal polymerization reaction, the base metal powder and the metal crosslinking agent eutectic phase polymerize under the action of a metal crosslinking initiator to form a new alloy phase.

[0036] According to some embodiments of the present invention, this reaction process utilizes chemical kinetics and thermodynamic properties to control the arrangement of atoms in the crystal, thereby regulating the mechanical properties of the alloy.

[0037] The inventors conducted a systematic study on the metal polymerization reaction described in this invention. During the metal polymerization reaction, the base metal powder and the eutectic phase of the metal crosslinking agent polymerize under the action of the metal crosslinking initiator to form a new alloy phase. Through the metal polymerization reaction, the liquid alloy and Fe, Co, Ni, Zn, Cu, Ti, V, and Cr (in aluminum alloys) transform into a solid alloy at room temperature, forming a completely new alloy structure (Figure 1). This reaction process utilizes chemical kinetics and thermodynamic properties to control the arrangement of atoms in the crystal, thereby regulating the mechanical properties of the alloy. The inventors verified the feasibility of using metal elements such as Fe, Co, Ni, Zn, Cu, Ti, V, and Cr using atomic orbitals. Simultaneously, they verified the formation principle of VIII, IB, and IIB transition elements in the 4th period, indicating that the distribution of electrons outside the nucleus of the elements exhibits the (Ar)3x-4sy-4pz pattern. The distribution of electrons outside the nucleus in the cycle follows the (Ar)3x-4sy-4pz pattern, where Ga, Fe, Co, Ni, Cu, and Zn are recorded as Ar(10-2-1)Ga, Ar(6-2-0)Fe, Ar(7-2-0)Co, Ar(8-2-0)Ni, Ar(9-2-0)Cu, and Ar(9-2-0)Zn, respectively. According to Hund's principle, Ar(6-2-0)Fe and Ar(10-2-1)Ga, during the formation of metallic bonds, combine with Ar((6-1)-(2-1)-0)Fe and Ar(10-2-(1+1+1))Ga, respectively, to form Ar(5-1-0)Fe and Ar(10-2-3)Ga. Similarly, Co-Ga, Ni-Ga, Cu-Ga and Zn-Ga respectively generate Ar(5-2-0)Co / Ar(10-2-3)Ga, Ar(5-2-0)Ni / Ar(10-2-3)Ga, Ar(10-2-0)Cu / Ar(10-2-0)Ga and Ar(10-1-0)Zn / Ar(10-1-3)Ga. The equations verified the energy conversion during the formation process.

[0038] Taking InGa3 as an example, the metal polymerization reaction results show that the initial two-dimensional InGa3 structure evolves into a three-dimensional liquid metal alloy structure. Free Ga atoms exist around the Ga-In-Ga-In-Ga chains of InGa3, and the resulting M-Ga phase (M being Fe, Co, Ni, Zn, Cu, Ti, V, and Cr) connects with the free Ga atoms on the chains. This restricts the inherent fluidity of the liquid metal, forming a 2.5-dimensional structure. Simultaneously, M reacts with InGa3, resulting in the formation of a fine-grained layer with a molten pool shape around the M particles. The formation process of the liquid metal alloy structure includes: 1) the material exhibits a polycrystalline state during printing, with grain sizes ranging from 0-200 μm; 2) the large crystal structure during the formation period is broken down, reducing the grain size to 0-8 μm; 3) during the refining period, the refined crystals recombine, forming a single-crystal structure with a size of approximately 70 μm, improving the mechanical properties of the liquid metal alloy structure.

[0039] This invention uses Cu3Al alloy as the base metal powder, InGa3 as the metal crosslinking agent, and NaOH aqueous solution as the metal crosslinking initiator to reveal the chemical change process of metal polymerization reaction mechanism.

[0040] First, the effect of the mass fraction of Cu3Al alloy and InGa3 on the metal polymerization reaction was verified. When the mass fraction of Cu3Al was below 30%, the metal polymerization reaction was difficult to proceed. However, when the mass fraction of Cu increased to 60%, the proportion of the CuGa2 phase increased with the increase of the Cu3Al mass fraction, and the polymerization reaction rate was relatively slow, suitable for processing in situations where the polymerization time is relatively slow. When the mass fraction of Cu3Al exceeded 60%, the metal polymerization reaction was relatively accelerated, suitable for applications requiring rapid polymerization and solidification. The optimal reaction performance was observed at a Cu3Al mass fraction of 60%, which is consistent with the X-ray diffraction results (Figure 2). The micro-stress and grain size of the obtained alloy were controlled by the mass fraction of Cu3Al; an appropriate Cu3Al mass fraction was beneficial for reducing micro-stress and grain size. With increasing diffraction angle, (InGa3)... 10 The grain size of the Cu6 liquid metal alloy underwent a smooth transition, while the micro-stress remained unchanged, indicating that the crystalline phase exhibits significant stability.

[0041] Electron backscattering diffraction was used to reveal (InGa3) 10The interaction between InGa3 and Cu3Al in the metal polymerization reaction of Cu liquid metal alloys (Figure 3). The refinement of Cu3Al grains through the substitution reaction of InGa3 represents a key process, leading to the refinement of Cu grains in the liquid metal alloy. During the dynamic evolution, fine CuGa2 particles spontaneously nucleate at the InGa3-Cu3Al interface. As the substitution reaction continues, the InGa3 phase on the InGa3 and Cu3Al substitution reaction products undergoes a significant substitution reaction, transforming into the CuGa2 solid phase, forming a solid-state structure. The substitution reaction sequence is enhanced by the solid solution strengthening effect of Ga (InGa3). 10 The crystal structure of Cu6 liquid metal alloy is improved, thereby enhancing its mechanical properties.

[0042] The nanostructure of (InGa3) was obtained using transmission electron microscopy and energy-dispersive X-ray fluorescence spectrometry, where InGa3 is mainly composed of Ga, In, and O. In the atomically enriched state, Ga undergoes significant oxidation, forming a Ga-O framework structure. In is embedded within the Ga-O framework and compressed by the introduction of Cu, resulting in a new CuGa2 phase, leading to In enrichment. Upon dissolution of the Ga-O framework, Cu and Ga are uniformly distributed within (InGa3). 10 On Cu6, InGa3 exhibits excellent crystallinity, clear diffraction patterns, and clear lattice fringes, presenting a nanoscale Cu-intercalated CuGa2 polycrystalline structure.

[0043] Traditional alloy 3D printing methods primarily include high-energy ion beam sintering and binder jet additive manufacturing. However, due to the high strength of metallic bonds, these processes typically require high temperatures (usually exceeding 1000°C) to break and reform these bonds during alloy preparation. Covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) polymerization have been widely applied in modern materials science. The question remains: does a covalent metal act as a bridge within a metal-metal framework (MMF) to facilitate metal-metal bond polymerization, ultimately forming a high-strength alloy? We have, for the first time, discovered alloy polymerization occurring at room temperature, similar to an AB bonding reaction (where A and B represent a metal crosslinking agent, exemplified by a eutectic gallium-indium alloy, and a base metal powder, respectively), where A and B, with the P6 / mmc space group, polymerize to form a novel high-strength alloy phase. Compared to conventional 3D-printed copper alloys, the resulting novel copper alloy exhibits superior mechanical properties, with an elastic modulus exceeding 130 GPa and a hardness exceeding 255 HV. This room-temperature alloy polymerization opens up a new method for alloy manufacturing, bridging the gap between the organic and metallic materials fields.

[0044] Using the method of this invention, liquid alloys can be transformed into solid alloys at room temperature, forming entirely new alloy structures. This process utilizes the chemical kinetics and thermodynamics of the reaction, and by controlling the material ratios, the mechanical properties of the alloy can be adjusted. The alloys obtained by this method not only possess excellent alloy strength and hardness, but also exhibit improved corrosion resistance and thermal stability, making them more competitive in industrial applications.

[0045] The novel metal polymer alloy obtained by the polymerization reaction of the present invention has high mechanical properties and broad industrial application prospects. Attached Figure Description

[0046] Figure 1 shows the microstructure of the polymer alloy obtained by metal polymerization of gallium-indium liquid alloy and aluminum alloy: MxAly (M represents Fe, Co, Ni, Zn, Cu, Ti, V and Cr). The first row is the scanning electron microscope image of the above aluminum alloy polymerization product, and the second row is the corresponding elemental distribution map.

[0047] Figure 2 shows the XRD patterns of polymer alloys obtained from Cu3Al alloys (copper-aluminum alloys) and InGa3 with different mass ratios (from bottom to top, the mass ratios of Cu3Al alloy to InGa3 are 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, and 100%).

[0048] Figure 3 shows the phase distribution of the alloy after metal polymerization when the mass ratio of Cu3Al alloy to InGa3 metal alloy is 60% (electron backscatter diffraction pattern EBSD).

[0049] Figure 4 shows transmission electron microscopy (TEM) images of the Cu3Al alloy and InGa3 metal alloy before and after metal polymerization when the mass ratio of Cu3Al alloy to InGa3 metal alloy is 60%.

[0050] Figure 5 shows (InGa3). 10 Figure showing the mechanical properties of Cu6.

[0051] Figure 6 shows (InGa3). 10 Comparison of mechanical properties of Cu6 with common metals.

[0052] Figures 7 and 8 show (InGa3). 10 The corrosion resistance test results of Cu6 (Figure 7 shows the open circuit potential results, and Figure 8 shows the polarization curve results).

[0053] Figure 9 shows a polymer alloy structural component obtained by 3D printing. Detailed Implementation

[0054] The present invention will be fully described below with reference to embodiments, which will provide a thorough understanding of the purpose, features, and effects of the invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention.

[0055] Example 1

[0056] A method for preparing a metal alloy includes the following steps:

[0057] 1) Cleaning: The base metal alloy MxAly (M is Fe, Co, Ni, Zn, Cu, Ti, V and Cr) (in the example, the mass percentage content of Al in MxAly is 25%, and the subscript indicates the mass ratio) powder is ultrasonically cleaned in 75% alcohol for 20 minutes, then dried in a vacuum dryer and stored in a vacuum seal.

[0058] 2) After ultrasonically cleaning the metal crosslinking agent in an aqueous solution containing hydroxide ions (pH value higher than 7.5) for 20 minutes, the basic salt solution was changed 3-4 times during this period until the basic salt solution used to clean the metal crosslinking agent became transparent. The surface residual basic salt was then rinsed with 75% alcohol, and subsequently stored in a 75% ethanol solution. In this paper, a 40% sodium hydroxide aqueous solution was used for the basic salt solution, and the metal crosslinking agent was a gallium-indium alloy.

[0059] 3) Place MxAly powder and the metal crosslinking agent in a glove box, fill it with N2 gas, open the reaction vessel containing MxAly and the metal crosslinking agent, and add a pH=9 aqueous solution of the metal crosslinking initiator to the reaction vessel. Add the metal crosslinking agent dropwise first, followed by MxAly. The aqueous solution of the metal crosslinking initiator used in this paper is a 0.00001 mol / L NaOH aqueous solution, and 1 g of metal crosslinking agent requires 0.02 g of sodium hydroxide.

[0060] 4) After mixing the base metal MxAly powder, metal crosslinking agent and metal crosslinking initiator evenly, remove the supernatant, seal and store, and react at room temperature (11~30℃) for 10~20min. The system will change from a fluid state to a solid state, and a new alloy material can be obtained.

[0061] In this embodiment, a Bruker D8 advanced X-ray diffractometer was used to verify 3D printing (InGa3). 10 Cu x The phase composition and crystal structure of liquid metal alloys are determined by this diffraction, which provides information on lattice constants and crystal orientation.

[0062] The (InGa3) was verified using a Chenhua CHE660E electrochemical workstation. 10 Cu xCorrosion resistance of liquid metal alloys.

[0063] A FEI Talos F200X transmission electron microscope and an energy dispersive spectrometer were used to examine (InGa3). 10 The nanostructure and elemental distribution of Cu6 liquid metal alloy were analyzed.

[0064] Electron backscatter diffraction (EBSD) measurements (InGa3) were performed using Verios 5 UC+Symmetry type. 10 Crystal size and distribution of Cu6 liquid metal alloy.

[0065] Nanoindentation tests (InGa3) were performed at room temperature using a U9820A nanoindentation analyzer. 10 Mechanical properties of Cu6 liquid metal alloy.

[0066] Figure 1 shows the scanning electron microscope image and elemental distribution map of the polymer alloy obtained by the above method, wherein the mass ratio of the base metal powder (MxAly alloy, where M is Fe, Co, Ni, Zn, Cu, Ti, V and Cr) to the metal crosslinking agent is 6:10.

[0067] Figure 2 shows the products obtained using Cu3Al alloy (Al content 25% by mass) as the base metal powder, InGa3 as the metal crosslinking agent, and 0.00001 mol / L NaOH aqueous solution as the metal crosslinking initiator. The mass ratios of Cu3Al alloy to InGa3 were 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, and 100% (numerator is the mass of Cu3Al alloy, denominator is the mass of InGa3). x Cu y The XRD pattern of (InGa3) was obtained. We can infer that the reactivity of the Cu3Al alloy is better when the addition amount is above 30%. The nanostructure of (InGa3) was obtained using transmission electron microscopy and energy-dispersive X-ray fluorescence spectrometry, where InGa3 is mainly composed of Ga, In, and O. In the atomically enriched state, Ga undergoes significant oxidation, forming a Ga-O framework structure. In is embedded in the Ga-O framework and compressed by the introduction of Cu, resulting in a new CuGa2 phase, leading to In enrichment. When the Ga-O framework structure dissolves, Cu and Ga are uniformly distributed in (InGa3). 10 On Cu6, InGa3 exhibits excellent crystallinity, clear diffraction patterns, and clear lattice fringes, presenting a nanoscale Cu-intercalated CuGa2 polycrystalline structure.

[0068] Figure 3 shows the alloy after metal polymerization when Cu3Al alloy is used as the base metal powder, InGa3 is used as the metal crosslinking agent, and 0.00001 mol / L NaOH aqueous solution is used as the metal crosslinking initiator, with a Cu3Al alloy:InGa3 mass ratio of 60% (polymerization product denoted as: (InGa3)). 10 The Cu6 phase distribution diagram is shown in the left and right images, which are electron backscattered diffraction (EBSD) patterns before and after polymerization, respectively. This invention uses electron backscattered diffraction to reveal the (InGa3) phase distribution. 10 The interaction between InGa3 and Cu3Al in the metal polymerization reaction of Cu6 liquid metal alloys. The key process is the refinement of Cu3Al grains through the substitution reaction of InGa3, which leads to the refinement of Cu grains in the liquid metal alloy. During the dynamic evolution, fine CuGa2 particles spontaneously nucleate at the InGa3-Cu3Al interface. As the substitution reaction continues, the InGa3 phase on the InGa3 and Cu3Al substitution reaction products undergoes a significant substitution reaction, transforming into the CuGa2 solid phase, forming a solid-state structure. The substitution reaction sequence is enhanced by the solid solution strengthening effect of Ga (InGa3). 10 The crystal structure of Cu6 liquid metal alloy is improved, thereby enhancing its mechanical properties.

[0069] Figure 4 shows the micrographs after metal polymerization using Cu3Al alloy as the base metal powder, InGa3 as the metal crosslinking agent, and 0.00001 mol / L NaOH aqueous solution as the metal crosslinking initiator, with a Cu3Al alloy:InGa3 mass ratio of 60%. The left and right images are transmission electron microscope images before and after polymerization, respectively.

[0070] Figure 5 shows (InGa3). 10 The mechanical properties of Cu6 are shown in Figure 6. Figure 6 shows the mechanical properties of (InGa3). 10 The comparison of the mechanical properties of Cu6 (Our work) with steel, non-ferrous metals (Mg, Cu, Al, Ti), and iron shows that the polymer alloy obtained in this invention has better mechanical properties. Figures 5 and 6 show that the indentation depth is 800 nm and the springback depth is 750 nm, indicating that the strain at this point reaches 6.3%. (InGa3) has a nano-hybrid structure. 10 The elastic modulus, nanohardness, and stiffness of Cu6 liquid metal alloy are 139.8, 2.69, and 6 × 10⁻⁶, respectively. 5 The N / m ratio is significantly higher than that of typical non-ferrous alloys, even slightly higher than cast iron, but slightly lower than that of forged steel. This is attributed to the constant pressure applied during formation, which promotes the transformation of fine-grained CuGa2 into a single-crystal structure, further enhancing the N / m ratio of (InGa3). 10 Mechanical properties of Cu6 liquid metal alloy.

[0071] Figures 7 and 8 show (InGa3). 10 Cu x The corrosion resistance results are shown in Figure 7. Figure 7 shows the measurement results for (InGa3). 10 Cu x The open-circuit potential (OCP) results for liquid metal alloys show that when the Cu mass fraction reaches 60%, the OCP is -1.3V, and InGa3 exhibits the most significant reducing properties, leading to an accelerated solid-phase formation rate.

[0072] Examples 2 to 5 illustrate several specific applications:

[0073] Example 2: Mold forming

[0074] 1) Cleaning: The basic metal powder Cu3Al powder was ultrasonically cleaned in 75% alcohol for 20 minutes, then dried in a vacuum dryer and stored in a vacuum seal.

[0075] 2) After ultrasonically cleaning the metal crosslinking agent gallium-indium alloy in a 40% sodium hydroxide aqueous solution for 20 minutes, the alkaline salt aqueous solution was changed 3-4 times during the process until the sodium hydroxide aqueous solution used to clean the metal crosslinking agent became transparent. The surface sodium hydroxide aqueous solution was then rinsed with 75% alcohol and stored in a 75% ethanol solution.

[0076] 3) Place Cu3Al powder and metal crosslinking agent alloy in a glove box, fill it with N2 gas, open the Cu3Al powder and metal crosslinking agent, add 0.00001mol / L NaOH aqueous solution to the reaction vessel, add the metal crosslinking agent dropwise first, then add Cu3Al powder, and mix evenly; the mass ratio of Cu3Al powder to metal crosslinking agent is 6:10, and 1g of metal crosslinking agent requires 0.02g of sodium hydroxide.

[0077] 4) Pour the mixture of Cu3Al powder and metal crosslinking agent into a mold, apply 100MPa pressure to the mixture using a press, hold the pressure for 24 hours, and then unload to obtain a polymer with mechanical properties.

[0078] Example 3: 3D Printing

[0079] When the ratio of Cu3Al powder to metal crosslinking agent is 4:10 (the amount of metal crosslinking agent initiator added is the same as in Example 2), the metal alloy has good fluidity above 30°C.

[0080] By controlling the temperature of the printing platform below 20°C, mechanical extrusion printing is performed using an EFL-BP6601 extrusion bioprinter. One barrel contains Cu3Al powder and a metal crosslinking agent, while the other barrel contains the metal crosslinking agent initiator.

[0081] Using a 16G plastic dispensing needle at a speed of 100 mm / min and a flow rate of 10 mL / min, a 3D solid structure was printed, as shown in Figure 9.

[0082] Example 4: Chemical Bolts

[0083] This embodiment provides a chemically bonded bolt made of metal polymer, using copper-aluminum alloy powder and gallium-indium alloy as raw materials. When the ratio of Cu3Al powder to the metal crosslinking agent gallium-indium alloy is 8:10 (the amount of metal crosslinking agent initiator added is the same as in Example 1), the metal alloy molding speed is 3-5 seconds, which can be used for bolt filling. When used on copper-based workpieces, this chemically bonded bolt can provide a tensile strength of 110 MPa, restoring 50% of its original mechanical strength. This chemically bonded bolt has acid resistance and high temperature resistance.

[0084] Example 5: High-frequency electromagnetic shielding coating

[0085] This embodiment 5 provides a metal polymerization method for the remanufacturing and repair of high-frequency electromagnetic shielding metal materials, using copper-aluminum alloy powder and gallium-indium alloy as raw materials (the amount of metal crosslinking agent and initiator added is the same as in embodiment 1). When the ratio of copper-aluminum alloy powder to metal crosslinking agent is 1:1, the metal polymerization has the characteristics of fast molding speed (within 3 seconds) and high-frequency electromagnetic fatigue.

[0086] Room temperature metal polymerization is used for the remanufacturing of high-frequency electromagnetic shielding metal materials to avoid high-temperature failure of the matrix material.

[0087] Example 6: Computer Heat Sink

[0088] Example 6 provides a thermally conductive liquid metal gel prepared by a metal polymerization method for cooling computer CPUs, using copper-aluminum alloy powder and gallium-indium alloy as raw materials (the amount of metal crosslinking agent and initiator added is the same as in Example 1). When the ratio of copper-aluminum alloy powder to metal crosslinking agent is 6:10, the fluidity of the liquid metal weakens, and it becomes a paste. At this time, the thermal conductivity is 120 W / m·K, which is much higher than that of commercial silicone grease (10 W / m·K).

Claims

1. A method of producing a metal alloy, characterized by, The method comprises the following steps: The base metal powder and the metal cross-linking agent are mixed under the action of the metal cross-linking initiator to obtain the metal alloy.

2. The method of claim 1, wherein the metal alloy is prepared by a method comprising: The method comprises the following steps: (1) Pre-treating the base metal powder and the metal cross-linking agent; (2) Mixing the pre-treated base metal powder, the metal cross-linking agent and the metal cross-linking initiator uniformly, and optionally removing the supernatant; (3) The base metal powder and the metal cross-linking agent are polymerized under the action of the metal cross-linking initiator to obtain the metal alloy.

3. The method of claim 1, wherein the metal alloy is prepared by a method comprising: The base metal powder is one or more of the following metals or metal alloys: Mg, Mg-Al alloy, Ti, Ti-Al alloy, V, V-Al alloy, Cr, Cr-Al alloy, Fe, Fe-Al alloy, Co, Co-Al alloy, Ni, Ni-Al alloy, Cu, Cu-Al alloy, Zn, Zn-Al alloy, Ag, Sn, Pt and Au; when the aluminum alloy is used, the mass percentage content of aluminum atoms is 5%-40%; the particle size of the base metal powder is 15-53 μm.

4. The method of producing a metal alloy according to claim 1, wherein The liquid metal is one or more of the following liquid metals: gallium-indium liquid metal, gallium-indium-zinc liquid metal, gallium-indium-tin liquid metal, gallium-indium-tin-bismuth liquid metal and gallium-indium-tin-zinc liquid metal.

5. The method of claim 1, wherein the metal alloy is prepared by a method comprising: The metal crosslinking initiator is an aqueous solution of one or more of sodium hydroxide, potassium hydroxide, aqueous ammonia, calcium hydroxide, a base having a cation that is a metal ion or NH 4+ a base having a cation that is a metal ion or NH 6. The method of making a metal alloy of claim 1, wherein, The mass ratio of the metal cross-linking agent to the base metal powder is 100:(30-100).

7. The method of making a metal alloy of claim 1, wherein, The mass ratio of the metal cross-linking initiator to the metal cross-linking agent is (0.01-0.1):

1.

8. The method of making a metal alloy of claim 1, wherein, The temperature of the metal polymerization reaction is 11-30 ℃.

9. The method of making a metal alloy of claim 1, wherein, The base metal powder is one or more of the following aluminum alloys corresponding to Fe, Co, Ni, Zn, Cu, Ti, V and Cr, and the mass percentage content of Al is 10%-35%; the metal cross-linking agent is a gallium-indium metal alloy; and the metal cross-linking initiator is sodium hydroxide.

10. A metal alloy, characterized by, The method comprises the following steps: The method comprises the following steps:

11. A method of processing a metal alloy structure, characterized by, The base metal powder, the metal cross-linking agent and the metal cross-linking initiator are mixed, and then poured into a corresponding mold, and optionally pressed to obtain the metal alloy structural member; Or the base metal powder, the metal cross-linking agent and the metal cross-linking initiator are mixed by using an extrusion printer to obtain the metal alloy structural member; Or the base metal powder, the metal cross-linking agents and the metal cross-linking initiator are directly coated on a target position for in-situ polymerization to obtain the metal alloy structural member. ​

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