Method for preparing multi-component liquid alloy through laser

Abstract

The invention discloses a method for preparing multi-component liquid alloy by laser at room temperature. The method comprises a substrate loaded with a precursor and a laser. The specific method comprises the following steps: firstly, uniformly mixing precursors of metal elements, further performing ultrasonic mixing on the precursors and liquid metal particles subjected to ultrasonic treatment, then transferring the mixture into a beaker, and performing laser synthesis and ultrasonic treatment in a liquid phase environment, so that the precursor salt is converted into the multi-element liquid alloy. The method is simple to operate, low in cost, mild in reaction condition, rapid, efficient, environment-friendly and pollution-free. The technology provided by the invention can realize the preparation of the multi-component liquid alloy at room temperature.

Description

Technical Field

[0001] This invention relates to liquid alloy preparation technology, and in particular to a method for preparing multi-component liquid alloys based on laser ablation technology.

[0002] Liquid alloys refer to multi-component metals that exist in a liquid state at room temperature. In addition to their high electrical conductivity, the liquid phase of these alloys also endows them with higher atomic mobility, excellent ductility, and a larger reaction surface area. Furthermore, introducing more metal elements into liquid alloys can achieve richer electronic structure control. However, the preparation of multi-component liquid alloys is still in its nascent stage. Unstable and inefficient preparation methods, as well as the limitation of element selection due to solubility, greatly restrict the research and application of this material in catalytic reactions, battery electrodes, and other fields. Therefore, it is necessary to explore other methods for preparing multi-component liquid alloys. Summary of the Invention

[0003] The technical problem to be solved by this invention is to provide a method for preparing multi-component liquid alloys using lasers. This method is simple to operate, low in cost, has mild reaction conditions, is rapid and efficient, and is environmentally friendly and pollution-free.

[0004] To achieve the above objectives, the present invention provides a method for preparing multi-component liquid alloys by laser ablation, comprising the following steps: (1) The liquid metal substrate was ultrasonically dispersed at room temperature in a liquid phase environment to obtain a primary suspension of metal particles with micro- and nano-sized particles. The particle size range was 50 nanometers to 2 micrometers. The ultrasonic power was above 30W, and 50W, 60W, and 70W were used in the experiment. The ultrasonic frequency was above 30kHz, and 30, 40, 50, and 60 kHz were used in the experiment. The ultrasonic duration was above 1h, and 1.5, 2, 3, and 4 hours were used in the experiment. The particle size distribution was 200 nanometers to 2 micrometers. Further extending the ultrasonic time could reduce the particle size to at least 50 nanometers. The degree of ultrasonic dispersion was only related to the total ultrasonic energy, and the ultrasonic power and frequency were not limited.

[0005] (2) Dissolve the metal precursor salt uniformly in a solvent, and then mix it with the primary suspension in step (1) by ultrasonic treatment at room temperature until uniformly mixed to form a secondary suspension; The purpose of sonication here is to mix the reactants evenly. The sonication power is above 30W, and 50W, 60W, and 70W were used in the experiment. The sonication frequency is above 30kHz, and 30, 40, 50, and 60 kHz were used in the experiment. The sonication duration is above 1 hour, and 1.5, 2, 3, and 4 hours were used in the experiment. The sonication time is 3-15 minutes.

[0006] (3) The secondary suspension after mixing in step (2) is transferred to a container and laser-treated in a liquid phase environment to obtain a multi-element liquid alloy; Furthermore, the following steps are adopted: (1) Select gallium or gallium-based liquid gold alloy with environmental friendliness and low melting point as substrate, and disperse it at room temperature in a liquid phase environment to obtain a primary suspension of liquid metal particles with micro-nano particle size.

[0007] (2) The precursor metal salt solution fitted into a multi-component liquid alloy is mixed evenly according to the stoichiometric ratio, and then ultrasonicated with the primary suspension in step (1) at room temperature until it is evenly mixed to form a secondary suspension.

[0008] To maintain its liquid state, gallium atoms comprise more than 60% of the total number of atoms, such as 65% or 70%.

[0009] (3) Transfer the secondary suspension from step (2) to a container (beaker), apply ultrasound in a liquid environment, and perform laser treatment.

[0010] The purpose of sonication here is to mix the reactants evenly. One experimental data point is that the ultrasonic power is 50W, the ultrasonic frequency is 40kHz, and the sonication time is 5 minutes.

[0011] Furthermore, the metallic elements involved in step (2) include any combination of platinum, gold, palladium, iridium, ruthenium, rhodium, cesium, copper, chromium, tin, iron, cobalt, nickel, zinc, manganese, vanadium, tantalum, tungsten, rhenium, osmium, hafnium, indium, rubidium, and strontium.

[0012] The precursor salts of the metal elements include chlorides, sulfates, phosphates, and nitrates; the solvents include, but are not limited to, ethanol, methanol, water, acetone, isopropanol, and carbon disulfide.

[0013] The preparation of multi-component liquid alloys was rapidly achieved under mild conditions. The experiments were conducted at room temperature and did not involve extreme temperatures, pressures, or other violent reaction conditions.

[0014] The gallium-based liquid metals involved in step (1) include gallium, indium, tin, as well as gallium-indium alloys, gallium-indium-tin alloys, etc.

[0015] Furthermore, the liquid environment described in step (2) includes various alkanes, methanol, ethanol, ethylene glycol, water, and isopropanol. To maintain the liquid state, the number of gallium atoms accounts for approximately 60% or more, and the mass fraction can be calculated based on the specific elements.

[0016] Lasers include, but are not limited to, nanosecond lasers and femtosecond lasers.

[0017] Laser processing parameters are power density 10 5 ~10 9W / cm 2 The frequency is within 80 kHz, and the duration of action is 3~24 h; the duration of laser action is set to 3~24 h according to the loaded metal element. Laser wavelengths cover ultraviolet, visible, and near-infrared light.

[0018] Beneficial effects: This invention significantly simplifies the cumbersome steps of synthesizing multi-component liquid alloys, achieving efficient and stable synthesis of multi-component liquid alloys in a simple and mild environment through laser ablation. This invention also allows for more flexible introduction of different metallic elements into the liquid alloy system. Attached Figure Description

[0019] Figure 1 The Ga synthesized in Specific Example 1 is the subject of this invention. 50 X-ray diffraction images of Pt liquid alloy; Figure 2A The Ga synthesized in Specific Example 1 is the subject of this invention. 50 Scanning electron microscope image of Pt liquid alloy (scale bar: 5 mm). Figure 2B 2C represents the elements Ga and Pt, respectively. Figure 2A Zhongga 50 Distribution map of Pt liquid alloy (scale bar: 5mm); Figure 3A , Figure 3B The Ga synthesized in Specific Example 1 is the subject of this invention. 50 X-ray photoelectron spectroscopy of Pt liquid alloy; among which... Figure 3A , 3B are the XPS spectra of Ga and Pt elements in the sample, respectively; Figure 4A The Ga synthesized in Specific Example 2 is the subject of this invention. 50 Scanning electron microscope image of Cu liquid alloy (scale bar: 2 mm). Figure 4B 4C represents Ga and Cu elements in Figure 4A Zhongga 50 Dispersion of Cu liquid alloy (scale bar: 2mm). Figure 5 The Ga synthesized in the specific embodiments of this invention relates to the present invention. 50 Another scanning electron microscope image of Pt liquid alloy (scale bar: 5 mm). Detailed Implementation

[0020] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments, but this should not be construed as limiting the scope of protection of the present invention. Example 1

[0021] This invention provides a method for preparing multi-component liquid alloys by laser ablation, comprising the following steps: (1) 0.6 g of metallic gallium was ultrasonically dispersed in 30 mL of ethanol at an ultrasonic power density of 15 W / L to obtain a primary suspension of metallic gallium micro- and nano-sized particles. The ultrasonic power was 50 W and the ultrasonic frequency was 40 kHz in the experiment; higher frequencies are also acceptable.

[0022] (2) 650 μL of 0.4 mol / L chloroplatinic acid in ethanol solution and the gallium nanoparticle suspension obtained in step (1) were ultrasonicated at room temperature until homogeneous to obtain a secondary suspension. Ultrasonication and mixing were carried out simultaneously, and the gallium metal would undergo a displacement reaction with the platinum in the chloroplatinic acid, which was not conducive to the subsequent synthesis of gallium-platinum alloy.

[0023] (3) Transfer the secondary suspension from step (2) to a beaker, and ablate the gallium nanoparticles precipitated at the bottom of the suspension using a nanosecond pulse laser with a pulse width of 5 ns. The average laser power density is set to 2 × 10⁻⁶. 5 W / cm 2 The frequency is 30kHz, the output power is set to 30%, and the laser wavelength is 1064nm, which belongs to the infrared band.

[0024] from Figure 1 As can be seen from the X-ray diffraction pattern, electron microscope image, and X-ray photoelectron spectrum in Figure 3, the Ga synthesized in Example 1... 50 In the Pt liquid alloy, Ga and Pt elements are uniformly dispersed in the bulk phase of the sample. Example 2

[0025] The difference between Example 2 and Example 1 is that Example 2 includes the following steps: (1) 0.6 g of metallic gallium was ultrasonically dispersed in 30 mL of ethanol to obtain a primary suspension of metallic gallium micro- and nano-sized particles.

[0026] (2) Mix 650 μL of 0.4 mol / L copper chloride in an ethanol solution with the gallium nanoparticle suspension obtained in step (1) by sonication at room temperature until homogeneous to obtain a secondary suspension.

[0027] (3) Transfer the secondary suspension from step (2) to a beaker, and ablate the gallium nanoparticles precipitated at the bottom of the suspension using a nanosecond pulse laser with a pulse width of 5 ns. The average laser power density is set to 2 × 10⁻⁶. 5 W / cm 2 The frequency is 30kHz, the output power is set to 30%, and the laser wavelength is 1064nm, which belongs to the infrared band.

[0028] As can be seen from the electron microscope image in Figure 4, the Ga synthesized in Example 2 50In the Cu liquid alloy, Ga and Cu elements are uniformly dispersed in the bulk phase of the sample. Example 3

[0029] The difference between Example 3 and Example 1 is that Example 3 includes the following steps: (1) 0.8 g of gallium indium tin alloy (available for purchase, composition of 68.5 wt % Ga, 21.5 wt % In and 10 wt % Sn) was ultrasonically dispersed in 30 mL of ethanol to obtain a primary suspension of gallium indium tin alloy micro-nano-sized metal particles.

[0030] (2) Mix 500 μL of 0.4 mol / L ferric nitrate in ethanol solution with the gallium indium tin alloy nanoparticle suspension obtained in step (1) by ultrasonication at room temperature until homogeneous to obtain a secondary suspension.

[0031] (3) Transfer the secondary suspension from step (2) to a beaker, and ablate the gallium indium tin alloy nanoparticles precipitated at the bottom of the suspension using a nanosecond pulse laser with a pulse width of 5 ns. The average laser power density is set to 2 × 10⁻⁶. 5 W / cm 2 The frequency is 30 kHz, the output power is set to 30%, and the laser wavelength is 1064 nm, which belongs to the infrared band. Example 4

[0032] The difference between Example 4 and Example 1 is that Example 4 includes the following steps: (1) 0.8g of gallium-indium alloy (available for purchase, composition of 75wt% Ga, 25wt% In) was ultrasonically dispersed in 30mL of ethanol and then dried to obtain gallium-indium alloy nanoparticles.

[0033] (2) Mix 500 μL of 0.4 mol / L cerium nitrate in ethanol solution with the gallium indium tin alloy nanoparticle suspension obtained in step (1) by ultrasonication at room temperature until homogeneous to obtain a secondary suspension.

[0034] (3) Transfer the secondary suspension from step (2) to a beaker, and ablate the gallium indium tin alloy nanoparticles precipitated at the bottom of the suspension using a nanosecond pulse laser with a pulse width of 5 ns. The average laser power density is set to 2 × 10⁻⁶. 5 W / cm 2 The frequency is 30 kHz, the output power is set to 30%, and the laser wavelength is 1064 nm, which belongs to the infrared band.

[0035] It should be noted that this method can be used to prepare liquid alloys with any combination.

[0036] The basic principles, main features, and advantages of this invention have been described above. Those skilled in the art should understand that this invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to this invention without departing from its spirit and scope. The scope of protection of this invention is defined by the appended claims, specification, and their equivalents.

Claims

1. A method for producing a multi-component liquid alloy by laser at room temperature, characterized by, The method comprises the following steps: (1) ultrasonic dispersion of liquid metal substrate in liquid phase environment at room temperature to obtain a primary suspension of micro-nano metal particles with a particle size ranging from 50 nm to 2 microns; (2) uniformly dissolving metal precursor salt in solvent, and then ultrasonic treating the primary suspension in step (1) to form a secondary suspension; (3) transferring the secondary suspension after mixing in step (2) to a container, and performing laser treatment in liquid phase environment to obtain a multi-element liquid alloy.

2. The method of claim 1, wherein the laser fabrication of the multi-component liquid alloy at room temperature is characterized by, The metal elements involved in step (2) include any combination of platinum, gold, palladium, iridium, ruthenium, rhodium, cesium, copper, chromium, tin, iron, cobalt, nickel, zinc, manganese, vanadium, tantalum, tungsten, rhenium, osmium, hafnium, indium, rubidium, strontium; the precursor salt of the metal elements includes chloride salt, sulfate salt, phosphate salt, nitrate salt.

3. The method of claim 1, wherein the laser is operated at room temperature. The method realizes the preparation of multi-element liquid alloy rapidly under mild conditions.

4. The method of claim 1, wherein: The liquid phase environment in step (1) includes ethanol, ethylene glycol, isopropyl alcohol.

5. The method of claim 1, wherein: The solvent in step (2) includes ethanol, ethylene glycol, water, acetone, isopropyl alcohol, carbon disulfide.

6. The method of claim 1, wherein: The liquid metal in step (1) includes gallium, indium, tin, gallium-indium alloy, gallium-indium-tin alloy.

7. The method of claim 1, wherein: The liquid phase environment in step (3) includes various alkanes, methanol, ethanol, ethylene glycol, water, isopropyl alcohol.

8. The method of claim 1, wherein: The laser processing parameters: power density is 10 5 ~10 9 W / cm 2 , frequency 1 Hz-80 kH, time length 3~24h; laser wavelength range covers ultraviolet, visible and infrared light.

Images