Silicate high-entropy amorphous material and preparation method thereof

Abstract

The invention provides a silicate high-entropy amorphous material and a preparation method thereof. The silicate high-entropy amorphous material is composed of silicate ions, sodium potassium alkali metal elements and the rest five metal elements. The material can be prepared by matching a simple hydrothermal method with a heat treatment process, the process is simple, and the material is suitable for large-scale production under the condition that new equipment and new technologies do not need to be introduced; meanwhile, compared with a conventional solid-phase high-temperature melting method, a laser melting supercooling method and other methods, the preparation method is smaller in energy consumption, low in preparation cost and beneficial to cost saving and environmental protection.

Description

Technical Field

[0001] The present invention belongs to the technical field of amorphous materials, and in particular relates to a silicate high entropy amorphous material and a preparation method thereof. Background Art

[0002] High entropy amorphous materials are an emerging class of materials with complex chemical compositions and disordered atomic structures. Unlike traditional alloys and crystalline materials, high entropy amorphous materials are usually composed of five or more elements in nearly equal molar ratios. The diversity of their constituent elements makes the materials highly disordered in their microstructure. Due to their unique element combination and disordered characteristics, high entropy amorphous materials exhibit excellent mechanical properties, good corrosion resistance, high temperature stability, and good magnetic and electrical properties. At the same time, since high entropy amorphous materials have many constituent elements, researchers can adjust the properties of materials by adjusting the types and proportions of elements, giving high entropy amorphous materials a wide range of application potential, huge design freedom, and very broad application prospects in aerospace, electronic equipment, energy storage and other fields. At present, high entropy amorphous materials mainly include high entropy alloy amorphous materials (CN103334065A) and high entropy metal oxide amorphous materials (CN108821571A), while high entropy amorphous materials of silicate systems have not yet been reported.

[0003] The preparation methods of high entropy amorphous materials mainly include the following: 1) Rapid cooling method: Avoid crystal formation by rapidly cooling the molten alloy to a solid state, including melt casting and spray cooling; 2) Sputtering deposition method: Using physical vapor deposition (PVD) technology, such as magnetron sputtering, to bombard the metal target to form a thin film, which is suitable for preparing high entropy amorphous materials in thin film form; 3) Laser melting method: Using laser to heat the material to a molten state, and then rapidly cooling it, you can obtain high entropy amorphous materials, which is suitable for small batch or customized production; 4) Chemical vapor deposition method: Generate amorphous materials through gas reaction, which can achieve precise composition control and is suitable for the preparation of high-purity materials; 5) Mechanical alloying method: Mix and grind multiple powders by mechanical means such as high-energy ball milling to promote the amorphization process. Although the current preparation methods are diverse, there are still some disadvantages: the preparation process of high entropy amorphous materials is complicated, especially in terms of composition design and process control, which has high requirements for equipment and technology; at the same time, due to the use of multiple elements and complex preparation processes, the current production cost of high entropy amorphous materials is high, which limits their large-scale application.

[0004] Therefore, developing a new system of high-entropy amorphous materials and studying a simple preparation method have become the focus of attention. Summary of the invention

[0005] In view of the problems existing in the background technology, the purpose of the present invention is to provide a silicate high entropy amorphous material and a preparation method thereof. The silicate high entropy amorphous material is composed of silicate ions, sodium potassium alkali metal elements and the remaining five metal elements; and the material can be prepared by a simple hydrothermal method combined with a heat treatment process, which is simpler and easier than the traditional amorphous preparation method and suitable for large-scale production.

[0006] To achieve the above object, the technical solution of the present invention is as follows:

[0007] A silicate high entropy amorphous material, the structural formula of which is (Na x K 1-x )(Al y M 1-y )Si 3 O 8±δ , wherein M is a combination of four metal elements, and the four metal elements are any four of Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, In, La, and Ce.

[0008] Furthermore, 0 <x<1,0.5≤y≤0.6,0<δ<1。

[0009] A method for preparing a silicate high entropy amorphous material comprises the following steps:

[0010] Step 1: Weigh sodium salt, potassium salt, silicon salt, aluminum salt and M metal salt according to the molar ratio of the elements;

[0011] Step 2: Place all the substances weighed in step 1 in a solvent, and then stir to fully dissolve them to obtain solution A;

[0012] Step 3: Add an aqueous ammonia solution to solution A and adjust the pH value to 10-12 to obtain solution B;

[0013] Step 4: placing solution B in a hydrothermal kettle for hydrothermal reaction, cooling naturally to room temperature after the reaction is completed, then pouring out the supernatant in the hydrothermal kettle, taking out the precipitate in the hydrothermal kettle, and then washing the precipitate to obtain a solid precursor material;

[0014] Step 5: Sinter the solid precursor material obtained in step 4 in an air atmosphere, and naturally cool to room temperature after sintering to obtain the desired silicate high entropy amorphous material.

[0015] Furthermore, the sodium salt is preferably sodium hydroxide, sodium nitrate, sodium sulfate or sodium acetate, the potassium salt is preferably potassium hydroxide, potassium nitrate, potassium sulfate or sodium potassium acetate, the silicon salt is preferably silicon tetrachloride, and the aluminum salt is preferably aluminum nitrate, aluminum sulfate, aluminum acetate; the M metal salt is preferably M nitrate, M sulfate, M acetate, M oxalate or ammonium salt.

[0016] Furthermore, in step 2, the solvent is preferably pure water or ethanol.

[0017] Furthermore, in step 4, the reaction temperature of the hydrothermal reaction is 120 to 220° C., and the reaction time is 10 to 16 hours.

[0018] Furthermore, in step 5, the sintering temperature is 400-800° C. and the sintering time is 12-24 hours.

[0019] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0020] The present invention prepares silicate high entropy amorphous materials based on alkali metal sources, silicon sources and other metal sources, and the preparation of the material can be achieved by combining hydrothermal reaction and solid-phase heat treatment. The process is simple and suitable for large-scale production without the need to introduce new equipment or new technology. At the same time, compared with conventional solid-phase high-temperature melting method, laser melting supercooling method and other methods, the preparation method of the present invention has lower energy consumption and low preparation cost, which is beneficial to cost saving and environmental protection. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is the XRD of silicate high entropy amorphous nanomaterials prepared by hydrothermal method in Example 1, Example 2 and Example 3.

[0022] Figure 2 TEM of silicate high entropy amorphous nanomaterials prepared by hydrothermal method in Example 1, Example 2 and Example 3;

[0023] Among them, (a) is Example 1, (b) is Example 2, and (c) is Example 3.

[0024] Figure 3 This is the electron diffraction spot pattern of the silicate high entropy amorphous nanomaterial prepared by the hydrothermal method in Example 1.

[0025] Figure 4 The XRD diagrams of the materials prepared in Comparative Examples 1 and 2 are shown. DETAILED DESCRIPTION

[0026] In order to make the objectives, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below in conjunction with the implementation modes and the accompanying drawings.

[0027] A silicate high entropy amorphous material, the structural formula of which is (Na x K 1-x )(Al y M 1-y )Si 3 O 8±δ , wherein M is composed of four metal elements, the molar ratios of the four metal elements are not much different, preferably the molar ratios of the four metal elements are the same, 0 <x<1,0.5≤y≤0.6,0<δ<1;

[0028] The metal elements are any four of Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, In, La, and Ce.

[0029] Example 1

[0030] A structural formula is (Na 0.5 K 0.5 )(Al 0.6 Cr 0.1 Mn 0.1 Fe 0.1 Co 0.1 )Si 3 O 8±δ The method for preparing a silicate high entropy amorphous material comprises the following steps:

[0031] Step 1. Sodium nitrate, potassium nitrate, silicon tetrachloride, aluminum sulfate, chromium nitrate, manganese nitrate, iron nitrate and cobalt nitrate are weighed respectively according to the molar ratio of elements Na:K:Si:Al:Cr:Mn:Fe:Co=0.5:0.5:3:0.6:0.1:0.1:0.1:0.1;

[0032] Step 2: Place all the substances weighed in step 1 into pure water and stir for 60 minutes to fully dissolve them to obtain solution A;

[0033] Step 3: Add an aqueous ammonia solution to solution A and adjust the pH value to 10 to obtain solution B;

[0034] Step 4: placing solution B in a hydrothermal kettle for hydrothermal reaction at a reaction temperature of 180°C for 12 hours; after the reaction is completed, naturally cooling to room temperature, then pouring out the supernatant in the hydrothermal kettle, taking out the precipitate in the hydrothermal kettle, and then washing the precipitate to obtain a solid precursor material;

[0035] Step 5: Sinter the solid precursor material obtained in step 4 in an air atmosphere at a sintering temperature of 700°C and a sintering time of 12 hours. After sintering, cool it naturally to room temperature and use a sieve to screen to obtain the silicate high entropy amorphous material of the desired target size.

[0036] Example 2

[0037] A structural formula is (Na 0.3 K 0.7 )(Al 0.5 Ca 0.1 Mg 0.1 Fe 0.2 Ti 0.1 )Si 3 O 8±δ The method for preparing a silicate high entropy amorphous material comprises the following steps:

[0038] Step 1. Weigh sodium hydroxide, potassium hydroxide, silicon tetrachloride, aluminum sulfate, calcium sulfate, magnesium nitrate, iron nitrate and titanium nitrate respectively according to the element molar ratio of Na:K:Si:Al:Ca:Mg:Fe:Ti=0.3:0.7:3:0.5:0.1:0.1:0.2:0.1;

[0039] Step 2: Place all the substances weighed in step 1 in ethanol and stir for 30 minutes to fully dissolve them to obtain solution A;

[0040] Step 3: Add an aqueous ammonia solution to solution A and adjust the pH value to 10 to obtain solution B;

[0041] Step 4: placing solution B in a hydrothermal kettle for hydrothermal reaction at a heating temperature of 140°C for 14 hours; after the reaction is completed, the solution is naturally cooled to room temperature, and then the supernatant in the hydrothermal kettle is poured out, the precipitate in the hydrothermal kettle is taken out, and then the precipitate is washed to obtain a solid precursor material;

[0042] Step 5: Sinter the solid precursor material obtained in step 4 in an air atmosphere at a sintering temperature of 500°C and a sintering time of 14 hours. After sintering, cool it naturally to room temperature and use a sieve to screen to obtain the silicate high entropy amorphous material of the desired target size.

[0043] Example 3

[0044] A structural formula is (Na 0.6 K 0.4 )(Al 0.6 Cr 0.1 Mn 0.1 Zn 0.1 Cu 0.1 )Si 3 O 8±δ The method for preparing a silicate high entropy amorphous material comprises the following steps:

[0045] Step 1. Weigh sodium hydroxide, potassium hydroxide, silicon tetrachloride, aluminum sulfate, chromium sulfate, manganese nitrate, zinc nitrate and copper nitrate respectively according to the element molar ratio of Na:K:Si:Al:Cr:Mn:Zn:Cu=0.6:0.4:3:0.6:0.1:0.1:0.1;

[0046] Step 2: Place all the substances weighed in step 1 into pure water and stir for 50 minutes to fully dissolve them to obtain solution A;

[0047] Step 3: Add an aqueous ammonia solution to solution A and adjust the pH value to 12 to obtain solution B;

[0048] Step 4: placing solution B in a hydrothermal kettle for hydrothermal reaction at a heating temperature of 200°C for 12 hours; after the reaction is completed, naturally cooling to room temperature, then pouring out the supernatant in the hydrothermal kettle, taking out the precipitate in the hydrothermal kettle, and then washing the precipitate to obtain a solid precursor material;

[0049] Step 5: Sinter the solid precursor material obtained in step 4 in an air atmosphere at a sintering temperature of 700°C and a sintering time of 12 hours. After sintering, cool it naturally to room temperature and use a sieve to screen to obtain the silicate high entropy amorphous material of the desired target size.

[0050] Comparative Example 1

[0051] The silicate high entropy amorphous material was prepared according to the steps of Example 1, except that the sintering temperature in step 5 was adjusted to 300° C., and the other steps remained unchanged.

[0052] Comparative Example 2

[0053] The silicate high entropy amorphous material was prepared according to the steps of Example 1, except that the sintering temperature in step 5 was adjusted to 900° C., and the other steps remained unchanged.

[0054] The XRD test results of the silicate high entropy amorphous materials prepared in Example 1, Example 2 and Example 3 are as follows: Figure 1 As shown, the XRD test results of the silicate materials prepared in Comparative Examples 1 and 2 are as follows Figure 2 The TEM characterization results of Example 1, Example 2 and Example 3 are shown in Figure 3 The electron diffraction pattern of the silicate high entropy amorphous material prepared in Example 1 is shown in Figure 4 shown.

[0055] from Figure 1 It can be seen that the diffraction peaks of the silicate high entropy amorphous materials prepared in the three embodiments are mantou peaks, and have typical characteristic X-ray diffraction spectra similar to amorphous materials, indicating that the preparation method of the embodiment of the present invention can successfully prepare high entropy amorphous oxide materials. Figure 2 It can be seen that the TEM images of the materials prepared in the three examples all show that the synthesized materials have no obvious orderly atomic arrangement, and mainly show a typical amorphous form of disordered atomic distribution. Figure 3 It can be seen that the material prepared in Example 1 presents a typical spot shape of an amorphous material, indicating that the preparation method of the embodiment of the present invention can successfully prepare nano-scale high-entropy amorphous oxide.

[0056] Figure 4 The XRD diagrams of the materials prepared in Comparative Examples 1 and 2 are shown. As can be seen from the figure, the temperature has a great influence on the preparation of amorphous materials. Higher or lower temperature will affect the crystal structure of the material, making it ordered to form crystals.

[0057] The above description is only a specific implementation mode of the present invention. Any feature disclosed in this specification, unless otherwise stated, can be replaced by other alternative features that are equivalent or have similar purposes; all the disclosed features, or all the steps in the methods or processes, except for mutually exclusive features and / or steps, can be combined in any way.

Claims

1. A silicate high entropy amorphous material, characterized in that: The structural formula of the silicate high entropy amorphous material is (Na x K 1-x )(Al y M 1-y )Si3O 8±δ , wherein M is a combination of four metal elements, and the four metal elements are any four of Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, In, La, and Ce.

2. The silicate high entropy amorphous material according to claim 1, characterized in that: 0 <x<1,0.5≤y≤0.6,0<δ<1。 3. A method for preparing a silicate high entropy amorphous material, characterized in that: The following steps are involved: Step 1: Weigh sodium salt, potassium salt, silicon salt, aluminum salt and M metal salt according to the molar ratio of the elements; Step 2: Place all the substances weighed in step 1 in a solvent, and then stir to fully dissolve them to obtain solution A; Step 3: Add an aqueous ammonia solution to solution A and adjust the pH value to 10-12 to obtain solution B; Step 4: placing solution B in a hydrothermal kettle for hydrothermal reaction, cooling naturally to room temperature after the reaction is completed, then pouring out the supernatant in the hydrothermal kettle, taking out the precipitate in the hydrothermal kettle, and then washing the precipitate to obtain a solid precursor material; Step 5: Sinter the solid precursor material obtained in step 4 in an air atmosphere, and naturally cool to room temperature after sintering to obtain the desired silicate high entropy amorphous material.

4. The preparation method according to claim 3, characterized in that: The sodium salt is sodium hydroxide, sodium nitrate, sodium sulfate or sodium acetate, the potassium salt is potassium hydroxide, potassium nitrate, potassium sulfate or sodium potassium acetate, the silicon salt is silicon tetrachloride, and the aluminum salt is aluminum nitrate, aluminum sulfate, aluminum acetate; the M metal salt is M nitrate, M sulfate, M acetate, M oxalate or ammonium salt.

5. The preparation method according to claim 3, characterized in that: In step 2, the solvent is pure water or ethanol.

6. The preparation method according to claim 3, characterized in that: In step 4, the reaction temperature of the hydrothermal reaction is 120 to 220° C., and the reaction time is 10 to 16 hours.

7. The preparation method according to claim 3, characterized in that: In step 5, the sintering temperature is 400-800° C. and the sintering time is 12-24 hours.

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