CN115819085A - Preparation method of aqueous phase precursor of high-entropy rare earth diboron carbide nano powder - Google Patents
Preparation method of aqueous phase precursor of high-entropy rare earth diboron carbide nano powder Download PDFInfo
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Abstract
The invention discloses a preparation method of a water-phase precursor of high-entropy rare earth diboron carbide nano powder, which comprises the following steps: weighing rare earth salt, a boron source and a carbon source according to a proportion; (2) Adding rare earth salt, a boron source and a carbon source into distilled water, and stirring at room temperature to fully dissolve the rare earth salt, the boron source and the carbon source to obtain a clear solution; (3) Fully drying the clear solution, and grinding to obtain precursor powder; (4) Performing hydraulic compaction on the precursor powder to obtain a densified blank; (5) And (3) carrying out normal-pressure high-temperature sintering treatment on the blank in vacuum or protective atmosphere to obtain the high-entropy rare earth diboron carbide nano powder. The invention prepares the high-entropy rare earth diboron carbide nano-powder by a water-phase precursor method, can effectively reduce the temperature of high-temperature reduction reaction, avoids using organic solvent and realizes the low-temperature environment-friendly preparation of the nano-powder.
Description
Technical Field
The invention relates to the technical field of high-entropy ceramic materials, in particular to a preparation method of a water-phase precursor of high-entropy rare earth diboron carbide nano-powder.
Background
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The ' high entropy ceramic ' is a new material design theory appearing in recent years, and as a near equimolar multi-component single-phase solid solution ceramic material, the unique ' high entropy effect ' of the ' high entropy ceramic can enable the material to show unique properties in certain aspects. Rare earth double boron carbide ceramic REB 2 C 2 (RE is rare earth element) has a typical lamellar structure, and the crystal structure of the (RE) lamellar structure is formed by a RE lamella and B 2 C 2 The rare earth double boron carbide ceramic is formed by alternate stacking in the c-axis direction, and the diversity of the elements which can be selected at the RE position lays a good foundation for preparing the high-entropy rare earth double boron carbide ceramic. At present, the existing reports mainly study the monopropellant YB 2 C 2 The related performance of the ceramic shows that YB 2 C 2 The ceramic has the advantages of high melting point, high strength, excellent damage tolerance and processability, good high-temperature stability and the like, and has wide application prospect in the fields of aerospace, national defense and military industry and the like.
The solid phase method is a commonly adopted method for preparing rare earth double boron carbide ceramics, and mainly comprises an element combination method and a high-temperature reduction reaction method. The element combination method is a method for synthesizing ceramic by directly carrying out combination reaction on elemental powder serving as a raw material at high temperature, but the use of the method is limited by the higher price of the rare earth elemental powder. The high-temperature reduction method comprises carbothermic reduction method and boron/carbothermic reduction method, and is prepared from oxide and C, B, B 4 C, reducing agent and the like are used as raw materials to synthesize ceramic powder through reduction reaction at high temperature. In order to improve the purity of the powder, the high-temperature reduction reaction must be fully carried out, so the synthesis of the rare earth diboron carbide ceramic usually needs to be kept at the temperature of more than 1800 ℃ for a certain time, but the long-time high-temperature treatment can cause the crystal grains to grow, the nano powder is difficult to prepare, and the sintering activity of the powder is reduced.
Aiming at the problems of the rare earth diboron carbide ceramics prepared by the solid phase method, a new preparation method of the high-entropy rare earth diboron carbide nano-powder needs to be explored urgently to solve the problems of high reaction temperature, large size of the obtained powder, poor sintering activity and the like of the solid phase high-temperature reduction reaction method.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing a water phase precursor of high-entropy rare earth diboron carbide nano powder, which is used for preparing the nano powder by a water phase precursor method, so that the use of an organic solvent can be avoided, and the low-temperature environment-friendly preparation of the nano powder is realized.
The technical scheme of the invention is as follows:
in a first aspect of the invention, a preparation method of a water-phase precursor of high-entropy rare earth diboron carbide nano-powder is provided, which comprises the following steps:
(1) Weighing rare earth salt, a boron source and a carbon source according to a proportion;
(2) Adding rare earth salt, a boron source and a carbon source into distilled water, and stirring at room temperature to fully dissolve the rare earth salt, the boron source and the carbon source to obtain a clear solution;
(3) Fully drying the clear solution, and grinding to obtain precursor powder;
(4) Performing hydraulic compaction on the precursor powder to obtain a densified blank;
(5) And (3) carrying out normal-pressure high-temperature sintering treatment on the blank in vacuum or protective atmosphere to obtain the high-entropy rare earth diboron carbide nano powder.
Preferably, the rare earth salt is a hydrochloride, nitrate or acetate corresponding to a rare earth element selected from at least three different elements of scandium, yttrium and lanthanoids, the molar ratio of each rare earth element being 1.
Preferably, the boron source is boron oxide or boric acid and the carbon source is sucrose or glucose.
Preferably, in the step (1), the rare earth salt, the boron source and the carbon source are respectively weighed according to the molar ratio of the sum of the rare earth metals, the boron element in the boron source and the carbon element in the carbon source of 1:5-7.
Preferably, in the step (3), the drying temperature of the clear solution is 90-200 ℃, and the drying time is 20-48 h.
Preferably, in the step (4), the hydraulic compaction pressure is 150 to 300MPa, and the dwell time is 5 to 15min.
Preferably, in step (5), the selected protective atmosphere is argon or helium.
Preferably, in the step (5), the sintering treatment is carried out at a temperature rise rate of 5-20 ℃/min to 1700-2000 ℃, and the heating is stopped after the temperature is kept for 1-5 h, so that the sintering treatment is cooled to room temperature along with the furnace.
Preferably, in the step (5), the temperature of the sintering treatment is increased to 1750-1850 ℃ at the heating rate of 10 ℃/min, and the heating is stopped after the temperature is kept for 1-2 h, so that the sintering treatment is cooled to the room temperature along with the furnace.
In the second aspect of the invention, the high-entropy rare earth diboron carbide nano powder is prepared by the aqueous phase precursor preparation method in the first aspect.
One or more technical schemes of the invention have the following beneficial effects:
(1) The invention adopts a water phase precursor method to prepare the high-entropy rare earth diboron carbide nano powder, realizes the mixing of reactants at the molecular level in a liquid environment, shortens the high-temperature reduction reaction path, effectively reduces the high-temperature reduction reaction temperature, can prepare the nano powder by adopting a simple process, and solves the problems of high reaction temperature, large size of the obtained powder, poor sintering activity and the like of a solid-phase high-temperature reduction reaction method.
(2) The synthetic route of the aqueous phase precursor provided by the invention can avoid the use of an organic solvent and realize the low-temperature environment-friendly preparation of the high-entropy rare earth diboron carbide nano-powder.
Drawings
FIG. 1 shows (Y) prepared in example 1 of the present invention 0.2 Sm 0.2 Gd 0.2 Ho 0.2 Er 0.2 )B 2 C 2 XRD pattern of the nano powder;
FIG. 2 is (Y) prepared in example 1 of the present invention 0.2 Sm 0.2 Gd 0.2 Ho 0.2 Er 0.2 )B 2 C 2 And (3) a transmission electron microscope morphology graph of the nano powder.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.
Aiming at the problems of the solid-phase high-temperature reduction reaction method, the invention provides a preparation method of a water-phase precursor of high-entropy rare earth diboron carbide nano-powder, which takes water-soluble rare earth salt, a carbon source and a boron source as raw materials, realizes the mixing of reactants in a molecular level in an aqueous solution, shortens the high-temperature reduction reaction path, reduces the high-temperature reduction reaction temperature, and simultaneously can avoid the use of an organic solvent and realize the low-temperature environment-friendly preparation of the nano-powder.
Example 1
(1) Weighing 10g of yttrium chloride, samarium chloride, gadolinium chloride, holmium chloride, erbium chloride, boron oxide and sucrose according to an element molar ratio of Y to Sm to Gd to Ho to Er to B to C = 1;
(2) Adding the substances into 70mL of distilled water, and stirring at room temperature for 24h to fully dissolve the substances to obtain a clear solution;
(3) Drying the clear solution at 150 ℃ for 24h, fully drying, and grinding to obtain precursor powder;
(4) Performing hydraulic compaction on the precursor powder (the pressure maintaining pressure is 200MPa, and the pressure maintaining time is 10 min) to obtain a densified blank;
(5) Placing the blank in a graphite crucible, placing the graphite crucible in a multifunctional sintering furnace, heating to 1800 ℃ at a speed of 10 ℃/min under the argon atmosphere, keeping the temperature for 1h, stopping heating, and cooling to room temperature along with the furnace to obtain (Y) 0.2 Sm 0.2 Gd 0.2 Ho 0.2 Er 0.2 )B 2 C 2 And (3) nano powder.
Fig. 1 is an XRD spectrum of the nano powder prepared in example 1, and it can be seen from fig. 1 that the obtained product is a pure single-phase solid solution.
FIG. 2 is a transmission electron microscope morphology image of the nano-powder prepared in example 1, and it can be seen from FIG. 2 that the size of the obtained powder is in the nano-scale.
Example 2
(1) Weighing 10g of yttrium chloride, ytterbium chloride, gadolinium chloride, dysprosium chloride, erbium chloride, boron oxide and glucose in a molar ratio of elements Y: yb: gd: dy: er: B: C = 1;
(2) Adding the substances into 60mL of distilled water, and stirring at room temperature for 20h to fully dissolve the substances to obtain a clear solution;
(3) Drying the clear solution at 140 ℃ for 24h, fully drying and grinding to obtain precursor powder;
(4) Performing hydraulic compaction on the precursor powder (the pressure maintaining pressure is 200MPa, and the pressure maintaining time is 10 min) to obtain a densified blank;
(5) Placing the blank in a graphite crucible, placing the graphite crucible in a multifunctional sintering furnace, heating to 1800 ℃ at a speed of 10 ℃/min under the argon atmosphere, preserving heat for 1h, stopping heating, and cooling to room temperature along with the furnace to obtain (Y) 0.2 Yb 0.2 Gd 0.2 Dy 0.2 Er 0.2 )B 2 C 2 And (3) nano powder.
Example 3
(1) Weighing 20g of yttrium chloride, cerium chloride, gadolinium chloride, dysprosium chloride, erbium chloride, boric acid and sucrose in a molar ratio of Y to Ce to Gd to Dy to Er to B to C = 1;
(2) Adding the substances into 120mL of distilled water, and stirring at room temperature for 24h to fully dissolve the substances to obtain a clear solution;
(3) Drying the clear solution at 180 ℃ for 30h, fully drying and grinding to obtain precursor powder;
(4) Performing hydraulic compaction on the precursor powder (the pressure maintaining pressure is 180MPa, and the pressure maintaining time is 10 min) to obtain a densified blank;
(5) Placing the blank in a graphite crucible, placing the graphite crucible in a multifunctional sintering furnace, heating to 1850 ℃ at 5 ℃/min under argon atmosphere, keeping the temperature for 2h, stopping heating, and cooling to room temperature along with the furnace to obtain (Y) 0.2 Ce 0.2 Gd 0.2 Dy 0.2 Er 0.2 )B 2 C 2 And (3) nano powder.
Example 4
(1) Weighing 15g of yttrium nitrate, samarium nitrate, gadolinium nitrate, holmium nitrate, erbium nitrate, boron oxide and sucrose according to an element molar ratio of Y to Sm to Gd to Ho to Er to B to C = 1;
(2) Adding the substances into 100mL of distilled water, and stirring at room temperature for 24h to fully dissolve the substances to obtain a clear solution;
(3) Drying the clear solution at 200 ℃ for 20h, fully drying, and grinding to obtain precursor powder;
(4) Performing hydraulic compaction on the precursor powder (the pressure maintaining pressure is 200MPa, and the pressure maintaining time is 10 min) to obtain a densified blank;
(5) Placing the blank in a graphite crucible, placing the graphite crucible in a multifunctional sintering furnace, heating to 1800 ℃ at a speed of 10 ℃/min under the argon atmosphere, keeping the temperature for 1h, stopping heating, and cooling to room temperature along with the furnace to obtain (Y) 0.2 Sm 0.2 Gd 0.2 Ho 0.2 Er 0.2 )B 2 C 2 And (3) nano powder.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a water phase precursor of high-entropy rare earth diboron carbide nano-powder is characterized by comprising the following steps:
(1) Weighing rare earth salt, a boron source and a carbon source according to a proportion;
(2) Adding rare earth salt, a boron source and a carbon source into distilled water, and stirring at room temperature to fully dissolve the rare earth salt, the boron source and the carbon source to obtain a clear solution;
(3) Fully drying the clear solution, and grinding to obtain precursor powder;
(4) Performing hydraulic compaction on the precursor powder to obtain a densified blank;
(5) And (3) carrying out normal-pressure high-temperature sintering treatment on the blank in vacuum or protective atmosphere to obtain the high-entropy rare earth diboron carbide nano powder.
2. The method for preparing the aqueous phase precursor of the high-entropy rare-earth diboron carbide nanopowder of claim 1, wherein the rare earth salt is a hydrochloride, a nitrate or an acetate corresponding to a rare earth element, the rare earth element is at least three different elements selected from scandium, yttrium and lanthanide elements, and the molar ratio of each rare earth element is 1.
3. The method for preparing the aqueous phase precursor of the high-entropy rare-earth diboron carbide nano-powder according to claim 1, wherein the boron source is boron oxide or boric acid, and the carbon source is sucrose or glucose.
4. The method for preparing the aqueous phase precursor of the high-entropy rare earth diboron carbide nano-powder according to claim 1, wherein in the step (1), the rare earth salt, the boron source and the carbon source are respectively weighed according to the molar ratio of the total rare earth metal, the boron element in the boron source and the carbon element in the carbon source of 1:5-7.
5. The preparation method of the aqueous phase precursor of the high-entropy rare-earth diboron carbide nano-powder according to claim 1, wherein in the step (3), the drying temperature of the clear solution is 90-200 ℃, and the drying time is 20-48 h.
6. The preparation method of the aqueous phase precursor of the high-entropy rare earth diboron carbide nanopowder of claim 1, wherein in step (4), the hydraulic compaction pressure is 150-300 MPa, and the pressure holding time is 5-15 min.
7. The method for preparing the aqueous phase precursor of the high-entropy rare earth diboron carbide nano-powder according to claim 1, wherein in the step (5), the selected protective atmosphere is argon or helium.
8. The preparation method of the aqueous phase precursor of the high-entropy rare earth diboron carbide nano-powder according to claim 1, wherein in the step (5), the sintering treatment is carried out, the temperature is increased to 1700-2000 ℃ at the temperature rising speed of 5-20 ℃/min, the temperature is kept for 1-5 h, and then the heating is stopped, so that the high-entropy rare earth diboron carbide nano-powder is cooled to the room temperature along with the furnace.
9. The method for preparing the aqueous phase precursor of the high-entropy rare earth diboron carbide nano-powder according to claim 8, wherein in the step (5), the sintering treatment is carried out, the temperature is increased to 1750-1850 ℃ at the temperature rising speed of 10 ℃/min, the temperature is kept for 1-2 h, and then the heating is stopped, so that the high-entropy rare earth diboron carbide nano-powder is cooled to the room temperature along with the furnace.
10. A high-entropy rare earth diboron carbide nano-powder is characterized in that: prepared by the method for preparing the water-phase precursor of any one of claims 1 to 9.
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