Method for forming solution contain metal, liquid solution and solid solution

Abstract

The present invention provides a method for forming a solution containing metal, which comprises: mixing a material containing metal and an ionic liquid to form a mixture; and stirring the mixture to form a first solution, wherein a ratio of the electrical conductivity of the first solution to the electrical conductivity of the material containing metal is lower than

Description

[Technical Field]

[0001] This invention relates to a method for forming a metal-containing solution, and more particularly to a method for forming a metal-containing solution by using an ionic liquid as a solvent. [Previous Technology]

[0002] Due to its excellent mechanical and chemical properties, such as high strength, high corrosion resistance, low friction coefficient, and near-theoretical elastic limit, metallic glass has become a promising new material in recent years. Compared to the conventional method of melting metallic glass, a better approach is to first dissolve the metallic glass to form a solution, and then use the solution containing the metallic glass for various processing procedures. This further expands the application scope of metallic glass, and the solution formation method is a more economical and promising approach.

[0003] Furthermore, in conventional techniques for forming solutions, inorganic acids are often used to dissolve metals. Examples of such inorganic acids include strong acids such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid. However, these strong acids are corrosive and environmentally unfriendly. Moreover, all known acids capable of dissolving metals react chemically with the metal during the dissolution process to produce salts. In other words, when using these inorganic acids as solvents to dissolve metals, it is impossible to dissolve and disperse the metal in a neutral molecular or atomic state within the solvent. In other words, if these inorganic acids are used to dissolve metallic glasses, the formation of metal salts also means that the glass structure is deconstructed, making it difficult for the resulting solution to reproduce the various excellent properties of the metallic glass in subsequent processing, thus limiting the application of metallic glasses.

[0004] In view of this, there is an urgent need for a method for dissolving metallic glass that can dissolve and disperse the metallic glass in a solvent in a state of uncharged molecules or atoms. [Summary of the Invention]

[0005] The present invention provides a method for forming a metal-containing solution, comprising: mixing a metal-containing material and an ionic liquid to form a mixture; and stirring the mixture to form a first solution, wherein the ratio of the conductivity of the first solution to the conductivity of the metal-containing material is less than 1.01.

[0006] In one specific embodiment of the present invention, the first solution is formed by stirring the mixture until the metal-containing material dissolves.

[0007] In one specific embodiment of the present invention, the first melt is subjected to heat treatment to form a second melt.

[0008] In a specific embodiment of the present invention, the first solution is a liquid solution and the second solution is a solid solution, that is, the first solution is a liquid and the second solution is a solid.

[0009] In one specific embodiment of the present invention, the mixing can be carried out at temperatures of 50 to 300°C, 50 to 200°C, 50 to 100°C, 50 to 90°C, 50 to 80°C, 50 to 70°C, 50 to 60°C, 60 to 100°C, 60 to 90°C, 60 to 80°C, 60 to 70°C, 70 to 100°C, 70 to 90°C, 70 to 80°C, 80 to 100°C, or 80 to 90°C. Of course, the mixing can also be stirred at temperatures of 100 to 300°C, 200 to 300°C, 100 to 200°C, 100 to 150°C, or any other temperature range.

[0010] In one specific embodiment of the present invention, the mixing time may be from 1 to 244 hours, at least 1 hour, at least 2 hours, at least 3 hours, at least 6 hours, at least 12 hours, at least 24 hours, at least 36 hours, at least 48 hours, at least 60 hours, at least 72 hours, at least 84 hours, at least 96 hours, at least 108 hours, at least 120 hours, at least 132 hours, at least 144 hours, at least 156 hours, at least 168 hours, at least 180 hours, or at least 192 hours. Of course, the mixing may also be stirred for 2 to 244 hours, or any other time range.

[0011] In one specific embodiment of the present invention, the temperature at which the heat treatment is applied may be 50 to 500°C, 50 to 400°C, 50 to 300°C, 50 to 200°C, 50 to 100°C, 50 to 90°C, 50 to 80°C, 50 to 70°C, 50 to 60°C, 60 to 100°C, 60 to 90°C, 60 to 80°C, 60 to 70°C, 70 to 100°C, 70 to 90°C, 70 to 80°C, 80 to 100°C, 80 to 90°C, 100 to 500°C, 100 to 400°C, 100 to 300°C, 100 to 200°C, 100 to 19°C. 0℃, 100 to 180℃, 100 to 170℃, 100 to 160℃, 100 to 150℃, 100 to 140℃, 100 to 130℃, 100 to 120℃, 100 to 110℃, 200 to 500℃, 200 to 400℃, 200 to 300℃, 200 to 290℃, 200 to 280℃, 200 to 270℃, 200 to 260℃, 200 to 250℃, 200 to 240℃, 200 to 230℃, 200 to 220℃, 200 to 210℃, 230 to 250℃, 235 to 245℃ or 220 to 260℃. Of course, the temperature at which this heat treatment is applied can also be 300 to 500°C, 400 to 500°C, 300 to 400°C, 300 to 350°C, or any other temperature range.

[0012] In one specific embodiment of the present invention, the duration of the heat treatment can be from 1 to 336 hours, at least 1 hour, at least 2 hours, at least 3 hours, at least 6 hours, at least 12 hours, at least 24 hours, at least 36 hours, at least 48 hours, at least 60 hours, at least 72 hours, at least 84 hours, at least 96 hours, at least 108 hours, at least 120 hours, at least 132 hours, at least 144 hours, at least 156 hours, at least 168 hours, at least 180 hours, at least 192 hours, at least 192 hours, at least 216 hours, at least 240 hours, at least 264 hours, at least 288 hours, at least 312 hours, or at least 336 hours. Of course, the duration of the heat treatment can also be from 2 to 336 hours, or any other arbitrary time range.

[0013] In one specific embodiment of the present invention, the metal in the metal-containing material includes bulk metallic alloy (BMG) or thin film metallic glass (TFMG).

[0014] In one specific embodiment of the present invention, the metal-containing material includes a substrate and a thin-film metallic glass, and the thin-film metallic glass is formed on the substrate by sputtering.

[0015] In one specific embodiment of the present invention, the method of forming a metal-containing solution further includes removing the substrate before mixing the metal-containing material and the ionic liquid.

[0016] In one specific embodiment of the present invention, the metal-containing material may be an alloy, which includes at least one metal selected from the group consisting of Zr (zirconium), Cu (copper), Al (aluminum), Ni (nickel), W (tungsten) and Pd (palladium).

[0017] In one specific embodiment of the present invention, the metal-containing material includes an alloy represented by formula (I):

[0017] M1xM2yM3zM4(100-xyz) formula (I).

[0018] In a specific embodiment of the present invention, in the above formula (I), any one of M1, M2, M3 and M4 is selected from Zr, Cu, Al, Ni, W or Pd, M1, M2, M3 and M4 are different from each other, x is between 50 and 70, y is between 15 and 35, and z is between 1 and 20.

[0019] In one specific embodiment of the present invention, the metal-containing material includes a metal alloy represented by formula (II):

[0019] ZrxCuyAlzNi(100-xyz) formula (II).

[0020] In a specific embodiment of the present invention, in the above formula (II), x is between 50 and 70, y is between 15 and 35, and z is between 1 and 20.

[0021] In a specific embodiment of the present invention, in the above formula (II), x is between 50 and 70, y is between 1 and 20, and z is between 15 and 35.

[0022] In a specific embodiment of the present invention, in the above formula (II), x is between 15 and 35, y is between 1 and 20, and z is between 50 and 70.

[0023] In a specific embodiment of the present invention, in the above formula (II), x is between 15 and 35, y is between 50 and 70, and z is between 1 and 20.

[0024] In a specific embodiment of the present invention, in the above formula (II), x is between 1 and 20, y is between 50 and 70, and z is between 15 and 35.

[0025] In a specific embodiment of the present invention, in the above formula (II), x is between 1 and 20, y is between 15 and 35, and z is between 50 and 70.

[0026] In one specific embodiment of the present invention, the metal-containing material includes an alloy represented by formula (III):

[0026] M5xM6yM7(100-xy) Equation (III).

[0027] In a specific embodiment of the present invention, in the above formula (III), any one of M5, M6 and M7 is selected from Zr, Cu, Al, Ni, W, Pd, Si (silicon), B (boron) or Y (yttrium), M5, M6 and M7 are different from each other, x is between 50 and 95, and y is between 3 and 25.

[0028] In one specific embodiment of the present invention, the metal-containing material includes an alloy represented by formula (IV):

[0028] WxNiyB(100-xy) Equation (IV).

[0029] In a specific embodiment of the present invention, in the above formula (IV), x is between 30 and 70, and y is between 20 and 30.

[0030] In a specific embodiment of the present invention, in the above formula (IV), x is between 20 and 30, and y is between 30 and 70.

[0031] In one specific embodiment of the present invention, the metal-containing material includes a metal alloy represented by formula (V):

[0031] PdxCuySi(100-xy) Formula (V).

[0032] In a specific embodiment of the present invention, in the above formula (V), x is between 60 and 80, and y is between 10 and 20.

[0033] In a specific embodiment of the present invention, in the above formula (V), x is between 10 and 20, and y is between 60 and 80.

[0034] In one specific embodiment of the present invention, the metal-containing material includes a metal alloy represented by formula (VI):

[0034] AlaNibY(100-ab) formula (VI).

[0035] In a specific embodiment of the present invention, in the above formula (VI), a is between 70 and 99, and b is between 0.01 and 30.

[0036] In one specific embodiment of the present invention, in the above formula (VI), a is between 0.01 and 30, and b is between 70 and 99.

[0037] In one specific embodiment of the present invention, the ionic liquid comprises a mixture selected from 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]), 1-butyl-3-methylimidazolium tetrafluorobromide ([BMIM][BF4]), 1-octyl-3-methylimidazolium hexafluorophosphate ([OMIM][PF6]), 1-octyl-3-methylimidazolium tetrafluoroborate ([OMIM][BF4]), and 1-decyl-3-methylimidazolium hexafluorophosphate. At least one ionic liquid from the group consisting of salts ([DMIM][PF6]), 1-decyl-3-methylimidazolium tetrafluoroborate ([DMIM][BF4]), 1-ethyl-3-methylimidazolium hexafluorophosphate ([EMIM][PF6]), 1-butyl-3-methylimidazolium trifluorosulfonate nitrogen salt ([BMIM][N(CF3SO2)2]), trihexyl(tetradecyl)phosphine bicyclic (2,4,4-trimethylpentyl) ([QP][Bis]), and trihexyl(tetradecyl)phosphonium chloride ([QP][Cl]).

[0038] In one specific embodiment of the present invention, the substrate is polyacrylonitrile (PAN) or polysulfone (PSF).

[0039] In a specific embodiment of the present invention, the first melt was analyzed by dynamic light scattering (DLS) and the particles in the first melt were found to have an average particle size of 100 to 600 nm and a polydisperse index (PDI) value of 0.42 to 0.92.

[0040] In a specific embodiment of the present invention, the ionic liquid has peak values ​​at 9.92, 8.81, 8.76, 5.46, 5.16, 4.70, 3.09, 2.53 and 2.09 ppm in the spectrum generated by H1 NMR analysis.

[0041] In a specific embodiment of the present invention, the spectrum generated by HCl NMR analysis of the first solution has peak values ​​at 10.13, 9.01, 8.95, 5.66, 5.36, 5.22, 3.28, 2.74 and 2.34 ppm.

[0042] In a specific embodiment of the present invention, all the peak positions in the spectrum generated by the C13 NMR analysis of the ionic liquid correspond to and are consistent with all the peak positions in the spectrum generated by the C13 NMR analysis of the first solution.

[0043] In a specific embodiment of the present invention, the second melt has diffraction peaks at 2θ of 12°, 15°, 20°, 25°, 27° and 30° in the spectrum generated by X-ray diffraction (XRD) analysis.

[0044] In a specific embodiment of the present invention, the spectrum generated by Fourier transform infrared spectroscopy (FTIR) analysis of the second melt has absorption peaks at 1171 cm⁻¹, 1463 cm⁻¹, 1468 cm⁻¹, 1570 cm⁻¹, 1581 cm⁻¹, 2871 cm⁻¹, 2955 cm⁻¹, 3109 to 3440 cm⁻¹, and 3562 cm⁻¹.

[0045] In a specific embodiment of the present invention, the spectrum generated by differential scanning calorimetry (DSC) analysis of the second melt shows an exothermic peak between 500 and 530°C.

[0046] The present invention further provides a method for recovering metals, including the steps described in the method for forming a metal-containing solution of the present invention. [Simplified Explanation of the Diagram]

[0047] Figures 1A to 1B are images of samples before and after immersion in solvent according to embodiments of the present invention.

[0048] Figure 1C is an image of a comparative example of the present invention before and after immersion in the solvent.

[0049] Figures 2A to 2D are spectra of ionic liquids and samples according to embodiments of the present invention, generated by DLS analysis.

[0050] Figures 3A to 3B are spectra of BMIM[BF4] ionic liquid and samples according to embodiments of the present invention, obtained by 1H NMR analysis.

[0051] Figure 3C is a spectrum generated by C13 NMR analysis of BMIM[BF4] ionic liquids and samples according to embodiments of the present invention.

[0052] Figure 4 is a spectrum generated by XRD analysis of a sample according to an embodiment of the present invention

[0053] Figure 5 is a spectrum generated by FTIR analysis of a sample according to an embodiment of the present invention.

[0054] Figure 6 is a spectrum generated by DSC analysis of a sample according to an embodiment of the present invention. [Implementation]

[0055] The embodiments of the present invention are illustrated below by means of specific specific embodiments, the advantages and efficacy of the invention may be readily understood by persons familiar with the art from what is revealed in this instruction manual.

[0056] It is noted that the structure, proportion, size, etc. shown in the diagrams attached to this instruction manual are for the purposes of understanding and reading by persons familiar with the technique only in conjunction with the content revealed in the instruction manual, and are not intended to limit the conditions under which the invention may be implemented. Therefore, without technical substantive significance, any modification of the structure, alteration of the proportional relationship or adjustment of size, without affecting the efficacy that the invention can produce and the purpose that can be achieved, shall remain within the scope of the technical content revealed by the invention can be covered. At the same time, terms such as “first”, “second”, “above”, “below” and “one” cited in this specification are for the purpose of facilitating the clarity of the account only and not to limit the scope of the present invention’s implementation. Furthermore, all ranges and values ​​in this paper are included and mergeable. Any numerical value or point that falls within the range described herein, such as any integer that can be used as a minimum or maximum value to derive a lower range.

[0057] The present invention provides a method of forming a metal-containing solution comprising: mixing a metal-containing material and an ionic liquid to form a mixture;

[0058] In another specific embodiment of the method for forming a metal-containing solution provided by the present invention, the method includes: forming a thin film of metallic glass on a substrate by sputtering to provide a metal-containing material, and providing an ionic liquid, wherein the ionic liquid includes [BMIM] ions; then mixing the metal-containing material and the ionic liquid to form a mixture; then dissolving the metal-containing material by stirring the mixture to form a first solution; and, if necessary, applying a heat treatment to the first solution to form a second solution.

[0059] In another specific embodiment of the present invention, the method for forming a metal-containing solution includes: providing a metal-containing material by sputtering a thin film of metallic glass onto a substrate, and providing an ionic liquid, wherein the ionic liquid includes [BMIM] ions; then removing the substrate; then mixing the metal-containing material and the ionic liquid to form a mixture; then stirring the mixture to dissolve the metal-containing material to form a first solution; and, if necessary, applying a heat treatment to the first solution to form a second solution.

[0060] Furthermore, according to the present invention, in the absence of heating, for example in an environment of 20 to 40°C, the ratio of the conductivity of the first melt to the conductivity of the metal-containing material is less than 1.01.

[0061] Preparation Examples 1 to 4: Composite materials including thin-film metallic glass coating

[0062] First to fourth targets are provided in the form of bulk metal alloys. Specifically, the first target is a Zr-based alloy target, the second target is a W-based alloy target, the third target is a Pd-based alloy target, and the fourth target is an Al-based alloy target. Further, the composition of the first target includes Zr60Cu25Al10Ni5, the composition of the second target includes W50Ni25B25, the composition of the third target includes Pd71.5Cu12Si16.5, and the composition of the fourth target includes Al95Ni3Y2. Furthermore, the first to fourth targets are all commercially available from Jiangyin Entre Coating Technology Co., Ltd., China.

[0063] A polysilicon substrate is provided, and magnetron sputtering is performed using first to fourth targets respectively. Specifically, under magnetron sputtering conditions where the distance between the target and the substrate is set to 100 mm, the gas pressure is 1.5 × 10⁻⁶ Pa, the working pressure is 4 mTorr, 100 W of DC power is supplied, and an Ar gas environment is provided, sputtering is performed using first to fourth targets respectively to form a thin film metallic glass coating on the polysilicon substrate.

[0064] Accordingly, thin-film metallic glasses of Preparation Examples 1 to 4 are provided, as shown in Table 1. Preparation Example 1 includes a Zr-based alloy thin-film metallic glass coating and a polyurethane substrate laminated structure; Preparation Example 2 includes a W-based alloy thin-film metallic glass coating and a polyurethane substrate laminated structure; Preparation Example 3 includes a Pd-based alloy thin-film metallic glass coating and a polyurethane substrate laminated structure; Preparation Example 4 includes an Al-based alloy thin-film metallic glass coating and a polyurethane substrate laminated structure.

[0065] Preparation Example 5: Powder including thin-film metallic glass

[0066] A sample of Preparation Example 1 with dimensions of 1.5 cm x 1.5 cm was provided and placed in a flask. Using N-methylpyrrolidone (NMP) as a solvent, NMP was poured into the flask containing the sample of Preparation Example 1 to dissolve and remove the polyurethane substrate. Next, a precipitate was obtained by vacuum filtration. The precipitate was washed several times with deionized water to remove the N-methylpyrrolidone, and then dried in a vacuum oven at 50°C for 12 hours. Finally, a sample of Preparation Example 9 was obtained, namely, a powder comprising a thin-film metallic glass.

[0067] As shown in Table 1, the first to fourth target materials and the composition of preparation examples 1 to 5 are detailed.

[0068] Table 1

[0069] Examples 1 to 4: Metal Dissolution Tests with Ionic Liquids

[0070] Using BMIM[BF4] ionic liquid (obtained from UNI-ONWARD corp) as the solvent, the samples of Preparation Examples 1 to 4 were immersed in BMIM[BF4] ionic liquid for 14 days. The dissolution was observed 1 day after immersion in the solvent and 14 days after immersion, and the results are recorded in Table 2. Figure 1A shows images of the samples in Examples 1 to 4 before immersion in the solvent and images of the samples 14 days after immersion in the solvent.

[0071] Examples 5 to 8: Metal Dissolution Tests with Ionic Liquids

[0072] Using BMIM[Cl] ionic liquid as a solvent, the samples of Preparation Examples 1 to 4 were immersed in BMIM[Cl] ionic liquid for 14 days. The dissolution was observed 1 day after immersion in the solvent and 14 days after immersion, and the results are recorded in Table 2. Figure 1B shows images of the samples in Examples 5 to 8 before immersion in the solvent and images of the samples 14 days after immersion in the solvent.

[0073] Comparative Examples 1 to 4: Metal Dissolution Test with Inorganic Acid

[0074] An appropriate volume of 1M HCl was used as the solvent, and the samples of Preparation Examples 1 to 4 were immersed in the HCl for 14 days. The dissolution was observed 1 day after the samples were immersed in the solvent and 14 days after the samples were immersed in the solvent. The observation results are recorded in Table 2. As shown in Figure 1C, the images of the samples in Comparative Examples 1 to 4 before they were immersed in the solvent and the images of the samples after they were immersed in the solvent for 14 days are shown.

[0075] As shown in Table 2, the observation results of the metal dissolution test of Examples 1 to 8 and Comparative Examples 1 to 4 are detailed.

[0076] Table 2

[0076] ◎: Completely dissolved

[0076] △: Partially dissolved

[0076] ×: No change

[0077] As shown in Table 2, the ionic liquids BMIM[BF4] and BMIM[Cl] have better metal dissolution capabilities than the inorganic acid HCl.

[0078] Examples 9 to 11

[0079] A sheet-like bulk metal alloy (BMG) was taken from the first target material as a solute, and BMIM[BF4] ionic liquid was used as a solvent. The solute was immersed in BMIM[BF4] ionic liquid. Under an inert nitrogen atmosphere, an oil bath at 75°C was used with magnetic stirring for 24 hours to obtain the solution (BMG-IL1) of Example 9.

[0080] Using the powder comprising thin-film metallic glass (TFMG) from Preparation Example 5 as the solute and BMIM[BF4] ionic liquid as the solvent, the solute was immersed in the BMIM[BF4] ionic liquid. Under an inert nitrogen atmosphere, the solution was prepared in an oil bath at 75°C with magnetic stirring for 24 hours to obtain the solution of Example 10 (TFMG-IL1). The preparation process of Example 10 was repeated using BMIM[Cl] ionic liquid instead of BMIM[BF4] as the solvent to obtain the solution of Example 11 (TFMG-IL2).

[0081] Further, based on the weight changes of the samples in Examples 9 to 11 before and after immersion, the weight percentage concentrations of solute and solvent in the solutions of Examples 9 to 11 were calculated respectively, and the calculation results are shown in Table 3.

[0082] The particle size distribution of BMIM[BF4] ionic liquid and the solutions of Examples 9 to 11 was analyzed using a Dynamic Light Scattering (DLS) analyzer (model: Zetasizer Nano Range (Nano-ZS90); manufacturer: Malvern). The analysis results are shown in Figures 2A to 2D. The conductivity of distilled water, BMIM[BF4] ionic liquid, the Zr-based metallic glass of Preparation Example 5, and the solution of Example 10 was analyzed using a conductivity analyzer (model: CON 700; supplier: EUTECH). The results are shown in Table 4. The solution of Example 9 and BMIM[BF4] ionic liquid were analyzed using a Nuclear Magnetic Resonance Spectroscopy (NMR Spectroscopy) (model: AV 500; supplier: United Kingdom) with deuterated dimethyl sulfoxide-d6 (DMSO-d6) as solvent.

[0083] As shown in Table 3, these are the weight percentage concentrations of solute and solvent in the solutions of Examples 9 to 11. Table 3 shows that the higher the concentration of the BMIM[BF4] ionic liquid, the less metal is dissolved.

[0084] Table 3

[0085] Figures 2A to 2D show the results obtained by dynamic light scattering (DLS) analysis of the BMIM[BF4] ionic liquid and the solutions of Examples 9 to 11. According to Figure 2A, the BMIM[BF4] ionic liquid has an average particle size of 138.5 nm and a polydispersity index (PDI) of 0.911. According to Figure 2B, the liquid solution of Example 9, formed from a sheet-like bulk metal alloy and the BMIM[BF4] ionic liquid, has an average particle size of 551.7 nm and a polydispersity index of 0.683. According to Figure 2C, the liquid solution of Example 10, formed from a powder including thin-film metallic glass (TFMG) and the BMIM[BF4] ionic liquid, has an average particle size of between 389.8 and a polydispersity index of 0.445. According to Figure 2D, the liquid solution of Example 11, formed from powder including thin film metallic glass (TFMG) and BMIM[Cl] ionic liquid, has an average particle size of 440 nm and a polydispersity index of 0.800.

[0086] Comparison of Figures 2A and 2C shows that before the metallic glass dissolves, the average particle size of the BMIM[BF4] ionic liquid is 138.5 nm, while the average particle size of the solution formed in Example 10 after the metallic glass dissolves increases to over 389.8 nm. Therefore, the dissolved metallic glass is dispersed in the ionic liquid as nanoparticles, rather than dissociating further into the solution after forming a salt with the ionic liquid. In other words, the dissolved metallic glass dispersed in the ionic liquid retains its original glass structure.

[0087] Comparison of Figures 2B and 2C shows that the liquid solution of Example 9, formed from sheet-like bulk metal alloy and BMIM[BF4] ionic liquid, has a larger average particle size and a higher polydispersity index value; the liquid solution of Example 10, formed from powder including thin-film metallic glass (TFMG) and BMIM[BF4] ionic liquid, has a smaller average particle size and a lower polydispersity index value (higher solution homogeneity). Accordingly, compared to sheet-like bulk metal alloy, the solubility of thin-film metallic glass (TFMG) powder in BMIM[BF4] ionic liquid is higher.

[0088] Comparison of Figures 2C and 2D shows that the liquid solution of Example 10, formed from powder including thin-film metallic glass (TFMG) and BMIM[BF4] ionic liquid, has a smaller average particle size and a lower polydispersity index (higher solution homogeneity); the liquid solution of Example 11, formed from powder including thin-film metallic glass (TFMG) and BMIM[Cl] ionic liquid, has a larger average particle size and a lower polydispersity index. Therefore, the BMIM[BF4] ionic liquid has better solubility than the BMIM[Cl] ionic liquid.

[0089] As shown in Figures 3A to 3B, the spectra of BMIM[BF4] ionic liquid and the solution of Example 10 are obtained by H1 NMR analysis. In the H1 NMR spectrum of BMIM[BF4] ionic liquid, peaks are present at 9.92, 8.81, 8.76, 5.46, 5.16, 4.70, 3.09, 2.53 and 2.09 ppm. In the H1 NMR spectrum of the first solution, peaks are present at 10.13, 9.01, 8.95, 5.66, 5.36, 5.22, 3.28, 2.74 and 2.34 ppm. As shown in Figure 3C, the spectra of BMIM[BF4] ionic liquid and the solution of Example 10 are obtained by C13 NMR analysis. The peak positions in the C13 NMR spectrum of the ionic liquid correspond to and are consistent with the peak positions in the C13 NMR spectrum of the first solution.

[0090] As shown in Table 4, the conductivity analysis results are obtained for distilled water, BMIM[BF4] ionic liquid, Zr-based metallic glass of Preparation Example 5 and solution of Example 10.

[0091] Table 4

[0092] As shown in Table 4, before the metallic glass dissolves, the conductivity of the Zr-based metallic glass in Preparation Example 5 is 8.5 × 10 μS × cm⁻¹, and the conductivity of the BMIM[BF₄] ionic liquid is 5.75 × 10³ μS. After the metallic glass dissolves, the conductivity of the solution formed in Example 10 is 8.53 × 10 μS. Comparing the conductivity of Preparation Example 5 and Example 10, it can be seen that the conductivity of the solution in Example 10 is similar to that of the Zr-based metallic glass before dissolution. Therefore, it can be inferred that the conductivity of the solution in Example 10 is dominated by the conductivity of the Zr-based metallic glass, and the Zr-based metallic glass does not significantly increase the conductivity of the solution formed due to dissolution. In other words, after the Zr-based metallic glass dissolves, the Zr-based metallic glass in the ionic liquid hardly forms salts with BMIM[BF₄] and does not dissociate, and the Zr-based metallic glass exists in the liquid solution of Example 10 in a non-charged state.

[0093] Example 12

[0094] The powder containing thin-film metallic glass (TFMG) from Preparation Example 5 was used as the solute, and BMIM[BF4] ionic liquid was used as the solvent. The solute was immersed in the solvent BMIM[BF4] ionic liquid. Under an inert nitrogen atmosphere, the solute was completely dissolved in an oil bath at 75°C with magnetic stirring for 192 hours (8 days) to obtain a liquid first solution. The liquid first solution was dried at 240°C for 288 hours (12 days) to obtain a second solution, which is a solid solution composed of metallic glass and ionic liquid (Example 12).

[0095] The solid melt of Example 12 was subjected to XRD diffraction analysis using an XRD analyzer (model: D2 PHASER X-ray Powder Diffractometer; supplier: Bruker, Karlsruhe, Germany); the solid melt of Example 12 was subjected to FTIR analysis using an FTIR spectrometer (model: Equinox 70 FT-IR; supplier: Bruker, Karlsruhe, Germany); and the solid melt of Example 12 was subjected to DSC analysis using a DSC analyzer.

[0096] As shown in Figure 4, the spectrum of the sample from Example 12 was generated by XRD analysis. As can be seen from Figure 4, in the spectrum of the sample from Example 11 generated by XRD analysis, there are diffraction peaks at 2θ of 12°, 15°, 20°, 25°, 27° and 30°.

[0097] As shown in Figure 5, the spectrum of the sample from Example 12 was generated by FTIR analysis. As can be seen from Figure 5, in the spectrum of the sample from Example 11 generated by FTIR analysis, absorption peaks exist at 1171 cm⁻¹, 1463 cm⁻¹, 1468 cm⁻¹, 1570 cm⁻¹, 1581 cm⁻¹, 2871 cm⁻¹, 2955 cm⁻¹, 3109 to 3440 cm⁻¹, and 3562 cm⁻¹.

[0098] As shown in Figure 6, the spectrum of the sample from Example 12 was generated by DSC analysis. As can be seen from Figure 6, there is an exothermic peak between 500 and 530°C in the spectrum of the sample from Example 12 generated by DSC analysis.

Claims

1. A method for forming a metal-containing solution, comprising: Mixing metallic materials and ionic liquids to form a mixture; as well as Stir the mixture to form a first melt. The ratio of the conductivity of the first melt to the conductivity of the metal-containing material is less than 1.

01.

2. The method as described in claim 1, further comprising, after forming the first melt, subjecting the first melt to heat treatment to form a second melt, wherein, The first solution is a liquid, and the second solution is a solid.

3. The method as described in claim 1, further comprising: Before mixing the metal-containing material and the ionic liquid, a thin film of metallic glass is formed on a substrate by sputtering; as well as Remove the substrate.

4. The method as described in claim 1, wherein, The metallic material includes alloys represented by formula (I): M1xM2yM3zM4(100-xyz) formula (I), Among them, M1, M2, M3 and M4 are selected from Zr, Cu, Al, Ni, W or Pd, M1, M2, M3 and M4 are different from each other, x is between 50 and 70, y is between 15 and 35, and z is between 1 and 20.

5. The method as described in claim 1, wherein, The metallic material includes alloys represented by formula (III): M5xM6yM7(100-xy) Equation (III), Among them, M5, M6 and M7 are selected from Zr, Cu, Al, Ni, W, Pd, Si, B or Y. M5, M6 and M7 are different from each other, x is between 50 and 95 and y is between 3 and 25.

6. The method as claimed in claim 1, wherein the ionic liquid comprises at least one selected from the group consisting of 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluorobromic acid, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-decyl-3-methylimidazolium hexafluorophosphate, 1-decyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluorosulfonate nitrogen salt, trihexyl(tetradecyl)phosphine bicyclic (2,4,4-trimethylpentyl) and trihexyl(tetradecyl)phosphonium chloride.

7. The method as described in claim 1, wherein, Dynamic light scattering (DLS) analysis of the first melt revealed that the particles in the first melt had an average particle size of 100 to 600 nm and a polydispersity index (PDI) of 0.42 to 0.

92.

8. The method as described in claim 1, wherein, The first lysate, as analyzed by 1H NMR, exhibited peaks at 10.13, 9.01, 8.95, 5.66, 5.36, 5.22, 3.28, 2.74, and 2.34 ppm.

9. The method as described in claim 1, wherein, All the peak positions in the spectrum generated by C13 NMR analysis of the ionic liquid correspond to and are consistent with all the peak positions in the spectrum generated by C13 NMR analysis of the first solution.

10. The method as described in claim 2, wherein, The XRD spectrum of the second melt showed diffraction peaks at 2θ of 12°, 15°, 20°, 25°, 27° and 30°.

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