CN114276148A - Hexagonal layered boride ceramic h-MAB material and preparation method thereof - Google Patents
Hexagonal layered boride ceramic h-MAB material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a hexagonal layered boride ceramic h-MAB material and a preparation method thereof, wherein the molecular formula of the h-MAB phase material is expressed as Mn+1ABnOr (MB)2zAx(MB2)yWherein M is selected from any one of IIIB, IVB, VB, VIB, VIIB and VIIIB elements, A is selected from any one of IIIA, IVA, VBA, VIA and VIIA elements, and B is boron element. The h-MAB phase material has a hexagonal structure. Wherein the transition metal boride unit MB and the A layer are alternately stacked. The preparation method comprises the following steps: and uniformly mixing the M, A and B powders according to a certain molar ratio, putting the mixture into a quartz tube after wrapping the uniformly mixed powders by using a molybdenum foil as a protective layer, and putting the quartz tube into a high-temperature tube furnace for reaction. The method is simple and effective, the raw materials are easy to obtain, the price is low,has important industrial application prospect. The invention also discloses the possible element space and chemical components of the h-MAB phase. The invention also discloses possible application of the h-MAB phase material, and the h-MAB phase material has good mechanical property, good conductivity, high hardness and the like.
Description
Technical Field
The invention belongs to the technical field of materials, relates to a novel inorganic material and a preparation method thereof, and relates to a hexagonal layered boride ceramic h-MAB material and a preparation method thereof.
Background
The binary transition metal borides have high hardness and high melting point, so that the binary transition metal borides have excellent electrical conductivity and thermal conductivity, and are expected to be applied to the fields of wear-resistant coatings, high-temperature structural materials, chemical catalysts, primary battery electrodes and the like (Inorg. chem.,2016,51, 11140; J.Am. chem. Soc.,2017,139,12915; J.Am. chem. Soc.,2017,139, 12370-12373). However, binary transition metal borides have limited application because of their low damage tolerance and fracture toughness, high processing cost, and most importantly, poor oxidation resistance in air. In 2015, Ade and Hillebrecht named a class of ternary transition metal borides with an orthorhombic structure as MAB phase, because of belonging to the orthorhombic system, abbreviated as "o-MAB phase" (inorg. chem., 2015, 54, 6122). The o-MAB phase is usually formed by alternating zigzag chains consisting of transition metal boride and A atom layers, and the MAB phase also shows different configurations according to the number of zigzag M-B chains and the number of A atom insertion layers, and the common 5 configurations, MAB and M2AB2,M3A2B2,M3AB4,M4AB6The general formula is (MB)2Ay(MB2)xM is transition metal element, A is mainly P area element, B is boron element. The o-MAB phase is similar to the MAX phase material, has the excellent performances of ceramic materials and metal materials, has high damage tolerance and easy processing, and can be used as a reinforcing phase of a composite material to improve the electric conductivity and the heat conductivity of the material.
Although the o-MAB phase has excellent properties similar to those of the MAX phase, currently, reports on the o-MAB phase are extremely limited, and the a element is mainly two main group elements of Al or Si, and the M element is also mainly a late transition metal element (int. The lack of MAB phase material limits the development and application of ternary transition metal borides. In 2019, the first ternary transition metal boride-Ti with a hexagonal crystal system is synthesized for the first time by a group of us2InB2It was found to have a typical layered structure similar to MAX, anAnd combines the excellent properties of metallic and ceramic materials (nat. comm.,2019,10, 2284). However, whether the novel hexagonal ternary transition metal boride can exist in a large amount stably like the MAX phase or not is a difficult problem which is troubling researchers.
Therefore, a novel transition metal boride material is developed, so that the transition metal boride material has rich traditional MAX phase types and good stability, and has important practical significance for wide application of ternary transition metal borides.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a hexagonal layered boride ceramic h-MAB material and a preparation method thereof.
Technical scheme
A hexagonal layered boride ceramic h-MAB material is characterized in that the h-MAB phase material has a hexagonal system and layered microstructure, and chemical bonds are adopted between layers; the molecular formula is represented as Mn+1ABnOr (MB)2zAx(MB2)yThe M is selected from any one of elements in IIIB, IVB, VB, VIB, VIIB and VIIIB groups, the A is selected from any one of elements in IIIA, IVA, VBA, VIA and VIIA, and the B is boron; wherein n is 1, 2 or 3, z is 1-2; x is 1-2; y is 0-2; the M isn+1ABnSpace groups include, but are not limited to, P63/mmc, R3m or
The (MB)2zAx(MB2)yIncluding but not limited to
The M includes but is not limited to any one or combination of several of Sc, Y, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and Mn elements.
The A includes but is not limited to any one or combination of several of Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, S or Se elements.
The form of the h-MAB phase material includes but is not limited to powder, block or film.
A method for preparing the hexagonal layer boride ceramic h-MAB material is characterized by comprising the following steps:
step 1, batching: the ratio of the M, A and B elements is 5:1:1-5:3:10, wherein the preferred ratio is 2:1:2-3:1: 4;
step 2: sintering by adopting a solid phase sintering method, an arc melting method or a molten salt method, wherein the sintering temperature is 300-3000 ℃, the sintering is carried out under the pressure of 0.1MPa-50GPa, and the reaction time under the reaction condition is 0.01-200h, so as to obtain the h-MAB phase.
The ratio of the M, A and B elements is 2:1:2-3:1: 4.
The sintering temperature is 700-.
The sintering pressure is 0.1MPa-20 GPa.
The reaction time is 0.01-72 h.
The use of the hexagonal layer boride ceramic h-MAB material is characterized in that: the h-MAB phase material is used as a coating material in an extreme working environment and as a precursor of a two-dimensional material.
Advantageous effects
The invention provides a hexagonal layered boride ceramic h-MAB material and a preparation method thereof, wherein the molecular formula of the h-MAB phase material is expressed as Mn+1ABnOr (MB)2zAx(MB2)yWherein M is selected from any one of elements in IIIB, IVB, VB, VIB, VIIB and VIIIB groups, A is selected from any one of elements in IIIA, IVA, VBA, VIA and VIIA, B is boron element, wherein n is 1, 2 or 3, and z is 1-2; x is 1-2; y is 0-2. The h-MAB phase material has a hexagonal structure. Wherein the transition metal boride unit MB and the A layer are alternately stacked. The preparation method comprises the following steps: and uniformly mixing the M, A and B powders according to a certain molar ratio, putting the mixture into a quartz tube after wrapping the uniformly mixed powders by using a molybdenum foil as a protective layer, and putting the quartz tube into a high-temperature tube furnace for reaction. The method is simple and effective, and has easily-accessible raw materials, low cost and high qualityThe industrial application prospect is promising. The invention also discloses the possible element space and chemical components of the h-MAB phase. The invention also discloses possible application of the h-MAB phase material, and the h-MAB phase material has good mechanical property, good conductivity, high hardness and the like.
Compared with the prior art, the invention has the main advantages that:
(1) the h-MAB phase material provided by the invention has a simple synthesis method, is highly matched with the h-MAB phase material, and has extremely strong expansibility.
(2) Compared with the existing o-MAB phase boride material, the h-MAB phase boride material provided by the invention has rich element space and shows more sufficient application prospect.
(3) The h-MAB phase material provided by the invention has a graphene-like boron layer, and the special crystal structure enables the (h-MAB phase) material to have novel physical properties, such as ultrahigh hardness, ultrahigh Young modulus and superconducting characteristics.
Drawings
FIG. 1 shows the preparation of example 1 in which the h-MAB phase material is Hf material2PbB XRD pattern;
FIG. 2 shows the preparation of example 1 in which the h-MAB phase material is Hf material2PbB;
FIG. 3 shows the preparation of example 1 in which the h-MAB phase material is Hf material2PbB high resolution transmission electron micrographs;
in the XRD pattern, the synthesized Hf is shown2PbB characteristic peak of powder material and theoretical predicted Hf2PbB the characteristic peaks of the crystals coincide well. Shows that we successfully prepare Hf2PbB and mixing the above powders. In the SEM image, we can see the Hf synthesized2PbB the powder exhibited a distinct layered structure, typical of ternary layered materials. In STEM, from [001 ]]The directions can show that Hf atoms and Pb atoms alternately appear in a nested equilateral triangle mode, the atom arrangement observed in the experiment is consistent with the atom arrangement rule of the calculation simulation, and the reliability of the experiment result is further explained.
FIG. 4 shows the preparation of example 2 in which the h-MAB phase material is Hf material2InB2An XRD pattern of (a);
FIG. 5 shows a preparation exampleThe material of the h-MAB phase in the 2-phase is Hf material2InB2Scanning the electronic picture map;
FIG. 6 shows the preparation of example 2 in which the h-MAB phase material is Hf material2InB2High resolution transmission electron microscopy images;
in the XRD pattern, the synthesized Hf is shown2InB2Characteristic peak of powder material and theoretical predicted Hf2InB2The characteristic peaks of the crystals coincide well. Shows that we successfully prepare Hf2InB2And (3) powder. In the SEM image, we can see the Hf synthesized2InB2The powder exhibits a distinct layered structure and is typically a ternary layered material. In STEM, from [001 ]]The directions can show that Hf atoms and In atoms alternately appear In a nested equilateral triangle mode, the atom arrangement observed In the experiment is consistent with the atom arrangement rule of the calculation simulation, and the reliability of the experiment result is further explained.
FIG. 7 shows that the h-MAB phase material in preparation example 3 is material V3PB4An XRD pattern of (a);
FIG. 8 shows that the h-MAB phase material in preparation example 3 is material V3PB4Scanning the electronic picture map;
FIG. 9 shows the preparation of example 3 in which the h-MAB phase material is material V3PB4High-resolution transmission electron microscope images of;
in the XRD pattern, synthetic V is shown3PB4Characteristic peak of powder material and V predicted by theory3PB4The characteristic peaks of the crystals coincide well. Shows that we successfully prepare V3PB4And (3) powder. In the SEM image, we can see the V that we synthesized3PB4The powder exhibits a distinct layered structure and is typically a ternary layered material. In the STEM diagram, it can be seen that the V atoms and the P atoms alternate in the form of nested equilateral triangles, and are from [100 ]]The V-P-V layer and the B layer appear alternately in the direction, and the atom arrangement observed in the experiment is consistent with the atom arrangement rule of the calculation simulation, so that the reliability of the experiment result is further explained.
FIG. 10 shows the preparation of example 8 in which the h-MAB phase material is material V3PB4XRD patterns of ceramic wafersA spectrum;
FIG. 11 shows that the h-MAB phase material in preparative example 8 is the material V3PB4Scanning electronic picture images of the ceramic wafer;
in the XRD pattern, synthetic V is shown3PB4Characteristic peak and theoretically predicted V of bulk material3PB4The characteristic peaks of the crystals coincide well. The XRD inset shows V3PB4Macroscopic picture of bulk material, demonstrating that we successfully produced V3PB4And (5) ceramic plates. In the SEM image, we can see the V that we synthesized3PB4The powder exhibits a distinct layered structure and is typically a ternary layered material.
FIG. 12 is a graph of mechanical properties of h-MAB phase predicted by first-order principle;
the mechanical properties of a series of h-MAB phases are simulated by first-principle calculation, and the mechanical properties of the h-MAB phases are found to meet M3AB4>M2AB2>M2And AB. Wherein V3PB4,Ti3SB4And the like exhibit high young's modulus and vickers hardness.
FIG. 13 is a graph of thermal performance of the first-order principle prediction of the h-MAB phase;
the first principle calculation simulates the ductility and brittleness and the thermodynamic performance of a series of h-MAB phases, and M is found3AB4And M2AB2The material is mainly represented by brittle material, and M2The AB material behaves mainly as a ductile material. M3AB4Exhibit excellent thermal properties such as high debye temperature, high melting point, and high thermal conductivity.
FIG. 14 first principles calculation predicts Hf2PbB and Hf2InB2The electronic structure of (1);
the first-nature principle calculation simulates h-MAB phase Hf2PbB and Hf2InB2Electron structure and electron density of states diagram of (1), Hf is seen in the diagram2PbB and Hf2InB2Is metallic conductive.
FIG. 15 is a Vickers hardness test chart of the h-MAB phase material V3PB4 in preparation example 8;
test V with Vickers hardness tester3PB4Vickers hardness of the block: (a) the figure shows V at a load of 500N3PB4The vickers hardness of the material was 1150HV (approximately 11GPa), and the indentation boundaries were clear and no cracks appeared. (b) The figure shows V at a load of 1000N3PB4The vickers hardness of the material was 1050HV (about 10GPa), and the indentation boundaries were clear and no cracks occurred.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
these examples are intended to illustrate the invention and are not intended to limit the scope of the invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.
Preparation example 1: in this embodiment, the h-MAB phase material is Hf material2PbB material.
The Hf is2PbB the preparation method of the powder is as follows:
(1) weighing hafnium powder (99%, 200 meshes), lead powder (99.99%, 300 meshes) and boron powder (99%, 325 meshes), grinding and mixing the materials according to the molar ratio of 2:1.1:1 to obtain a mixture.
(2) And (3) putting the mixture into a quartz tube after wrapping the uniformly mixed powder by using a molybdenum foil as a protective layer, and putting the quartz tube into a high-temperature tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1100 ℃, the heat preservation time is 30 hours, and the inert atmosphere is used for protection. And after the temperature of the tube furnace is reduced to the room temperature, taking out the reaction product in the quartz tube. The sintered powder was ground in an agate mortar and sieved through a 200 mesh sieve (pore size 74 μm).
(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then cleaning the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a solid product.
FIG. 1 shows Hf obtained after the reaction2PbB, it can be seen that the product obtained is a 211 configuration h-MAB phase with some impurity phases. FIG. 2 shows reacted Hf2PbB, which exhibited a smooth surfaced plate-like morphology, similar to the MAX phase morphology previously reported. FIG. 3 is a microstructure diagram of atomic scale under STEM and a crystal structure predicted by the first principle, from which it can be seen that Hf atoms and Pb atoms are arranged in a hexagonal shape, which is consistent with the atom arrangement in the crystal structure predicted by theory, and illustrates that we have successfully prepared Hf2PbB material.
Preparation example 2: in this embodiment, the h-MAX phase material is Hf material2InB2A material.
(1) Weighing hafnium powder (99%, 200 meshes), indium powder (99.99%, 200 meshes) and boron powder (99%, 325 meshes), grinding and mixing the materials according to the molar ratio of 2.1:1:2 to obtain a mixture.
(2) And (3) putting the mixture into a quartz tube after wrapping the uniformly mixed powder by using a molybdenum foil as a protective layer, and putting the quartz tube into a high-temperature tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1100 ℃, the heat preservation time is 36 hours, and the inert atmosphere is used for protection. And after the temperature of the tube furnace is reduced to the room temperature, taking out the reaction product in the quartz tube. The sintered powder was ground in an agate mortar and sieved through a 200 mesh sieve (pore size 74 μm).
(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then cleaning the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a solid product.
FIGS. 4 and 5 are Hf obtained after the reaction2InB2The obtained product is the h-MAB phase with 212 configuration and partial impurity phase, and the sample shows a plate-like morphology with smooth surface, which is similar to the previously reported Ti2InB2The phase morphology is similar. FIG. 6 is a microstructure diagram at an atomic scale under STEM and a theoretically predicted crystal structure, from which Hf atoms andthe In atoms are arranged In a hexagon, which indicates that we successfully prepare Hf2PbB material.
Preparation example 3 in this example, the h-MAX phase material is the material V3PB4A material.
(1) Vanadium powder (99.5%, 325 mesh), phosphorus powder (98.5%, 200 mesh) and boron powder (99%, 325 mesh) are weighed, and the materials are ground and mixed according to the molar ratio of 3:1:4 to obtain a mixture.
(2) And (3) putting the mixture into a quartz tube after wrapping the uniformly mixed powder by using a molybdenum foil as a protective layer, and putting the quartz tube into a high-temperature tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1050 ℃, the heat preservation time is 30 hours, and the inert atmosphere is used for protection. And after the temperature of the tube furnace is reduced to the room temperature, taking out the reaction product in the quartz tube. The sintered powder was ground in an agate mortar and sieved through a 200 mesh sieve (pore size 74 μm).
(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then cleaning the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a solid product.
FIGS. 7, 8 and 9 show V obtained after the reaction3PB4As can be seen from the XRD patterns, SEM patterns and STEM patterns, the obtained product was a 314-configuration h-MAB phase with a portion of impurity phase, and the sample exhibited a plate-like morphology with a smooth surface, similar to the h-MAB phase morphology synthesized in examples 1 and 2. From FIG. 9, it can be seen that the V atoms and P atoms are in a hexagonal arrangement, indicating that we have successfully prepared V3PB4A material.
Preparation example 4: in this embodiment, the h-MAB phase material is Hf material2BiB material.
The Hf is2PbB the preparation method of the powder is as follows:
(1) weighing hafnium powder (99%, 200 meshes), bismuth powder (99.99%, 300 meshes) and boron powder (99%, 325 meshes), grinding and mixing the materials according to the molar ratio of 2:1.2:1 to obtain a mixture.
(2) And (3) putting the mixture into a quartz tube after wrapping the uniformly mixed powder by using a molybdenum foil as a protective layer, and putting the quartz tube into a high-temperature tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1100 ℃, the heat preservation time is 30 hours, and the inert atmosphere is used for protection. And after the temperature of the tube furnace is reduced to the room temperature, taking out the reaction product in the quartz tube. The sintered powder was ground in an agate mortar and sieved through a 200 mesh sieve (pore size 74 μm).
(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then cleaning the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a solid product.
Preparation example 5 in this example, the h-MAB phase material was material V2PB2A material.
(1) Vanadium powder (99.5%, 325 mesh), phosphorus powder (98.5%, 200 mesh) and boron powder (99%, 325 mesh) are weighed, and the materials are ground and mixed according to the molar ratio of 2:1:2 to obtain a mixture.
(2) And (3) putting the mixture into a quartz tube after wrapping the uniformly mixed powder by using a molybdenum foil as a protective layer, and putting the quartz tube into a high-temperature tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1050 ℃, the heat preservation time is 30 hours, and the inert atmosphere is used for protection. And after the temperature of the tube furnace is reduced to the room temperature, taking out the reaction product in the quartz tube. The sintered powder was ground in an agate mortar and sieved through a 200 mesh sieve (pore size 74 μm).
(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then cleaning the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a solid product.
Preparation example 6 in this example, the h-MAB phase material was Nb2PB2A material.
(1) Weighing niobium powder (99.5%, 325 mesh), phosphorus powder (98.5%, 200 mesh) and boron powder (99%, 325 mesh), grinding and mixing the materials according to the molar ratio of 2:1:2 to obtain a mixture.
(2) And (3) putting the mixture into a quartz tube after wrapping the uniformly mixed powder by using a molybdenum foil as a protective layer, and putting the quartz tube into a high-temperature tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1050 ℃, the heat preservation time is 32 hours, and the inert atmosphere is used for protection. And after the temperature of the tube furnace is reduced to the room temperature, taking out the reaction product in the quartz tube. The sintered powder was ground in an agate mortar and sieved through a 200 mesh sieve (pore size 74 μm).
Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then cleaning the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a solid product.
Preparation example 7 in this example, the h-MAB phase material was Nb2PB2A material.
(1) Weighing niobium powder (99.5%, 325 mesh), phosphorus powder (98.5%, 200 mesh) and boron powder (99%, 325 mesh), grinding and mixing the materials according to the molar ratio of 2:1:2 to obtain a mixture.
(2) And (3) putting the mixture into a quartz tube after wrapping the uniformly mixed powder by using a molybdenum foil as a protective layer, and putting the quartz tube into a high-temperature tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1050 ℃, the heat preservation time is 32 hours, and the inert atmosphere is used for protection. And after the temperature of the tube furnace is reduced to the room temperature, taking out the reaction product in the quartz tube. The sintered powder was ground in an agate mortar and sieved through a 200 mesh sieve (pore size 74 μm).
Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then cleaning the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a solid product.
Preparation example 8 in this example, the h-MAB phase material was the materialV3PB4And (3) a block body.
(1) Vanadium powder (99.5%, 325 mesh), phosphorus powder (98.5%, 200 mesh) and boron powder (99%, 325 mesh) are weighed, and the materials are ground and mixed according to the molar ratio of 3:1:4 to obtain a mixture.
(2) And placing the mixture in a cold isostatic press for static pressure forming, and keeping the load for 30 seconds at 5MPa to obtain a blank with the diameter of 2 cm. And then wrapping the blank by using graphite paper, and putting the blank into a hot-pressing furnace for reaction. The reaction conditions are as follows: raising the temperature from room temperature to 1050 ℃ at the speed of 5 ℃/min, simultaneously applying the pressure of 30MPa, keeping the temperature for 2 hours, and protecting by inert atmosphere. And after the temperature of the tube furnace is reduced to the room temperature, taking out the reaction product wrapped by the graphite paper. Grinding graphite on the surface of the block body by using abrasive paper to obtain V3PB4And (5) ceramic plates.
(3) Will V3PB4And (3) inlaying the ceramic wafer in a hot inlaying machine, sequentially polishing the surface of the ceramic wafer by using 70-1500-mesh sand paper until a smooth mirror surface is obtained, and carrying out hardness test.
FIGS. 10 and 11 show V obtained after the reaction3PB4The XRD and SEM images of the obtained product are 314 h-MAB phase and partial impurity phase, and the sample shows a plate-shaped appearance with smooth surface, which is similar to the powder V synthesized in example 33PB4The phase morphology is similar.
The properties of the h-MAB phase materials obtained by the practice of the invention 4-7 are substantially identical to those of the products of examples 1-3. In addition, the inventor also replaces the corresponding raw materials and process conditions In the above embodiments 1-7 with other raw materials and process conditions mentioned In the present specification, and has conducted relevant experiments, for example, a is replaced by Al, In, Ge, Si, S, As, etc., and M is replaced by Sc, Y, Ti, Nb, Ta, etc., and the results show that h-MAB phase materials can be prepared.
Compared with the existing MAX phase and o-MAB phase materials, the h-MAB phase material implemented by the invention has the advantages of excellent performances of both metal materials and ceramic materials, universality in preparation method, wide raw material source and potential application prospect in the fields of high-temperature heat-resistant and pressure-resistant devices, coating candidate materials and the like.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. A hexagonal layered boride ceramic h-MAB material is characterized in that the h-MAB phase material has a hexagonal system and layered microstructure, and chemical bonds are adopted between layers; the molecular formula is represented as Mn+1ABnOr (MB)2zAx(MB2)yThe M is selected from any one of elements in IIIB, IVB, VB, VIB, VIIB and VIIIB groups, the A is selected from any one of elements in IIIA, IVA, VBA, VIA and VIIA, and the B is boron; wherein n is 1, 2 or 3, z is 1-2; x is 1-2; y is 0-2; the M isn+1ABnSpace groups include, but are not limited to, P63/mmc, R3m or
The (MB)2zAx(MB2)yIncluding but not limited to
2. The hexagonal layered boride ceramic h-MAB material of claim 1, characterized in that: the M includes but is not limited to any one or combination of several of Sc, Y, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and Mn elements.
3. The hexagonal layered boride ceramic h-MAB material of claim 1, characterized in that: the A includes but is not limited to any one or combination of several of Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, S or Se elements.
4. The hexagonal layered boride ceramic h-MAB material of claim 1, characterized in that: the form of the h-MAB phase material includes but is not limited to powder, block or film.
5. A method for preparing the hexagonal layered boride ceramic h-MAB material according to any one of claims 1 to 4, characterized by the following steps:
step 1, batching: the ratio of the M, A and B elements is 5:1:1-5:3:10, wherein the preferred ratio is 2:1:2-3:1: 4;
step 2: sintering by adopting a solid phase sintering method, an arc melting method or a molten salt method, wherein the sintering temperature is 300-3000 ℃, the sintering is carried out under the pressure of 0.1MPa-50GPa, and the reaction time under the reaction condition is 0.01-200h, so as to obtain the h-MAB phase.
6. The method of claim 5, wherein: the ratio of the M, A and B elements is 2:1:2-3:1: 4.
7. The method of claim 5, wherein: the sintering temperature is 700-.
8. The method of claim 5, wherein: the sintering pressure is 0.1MPa-20 GPa.
9. The method of claim 5, wherein: the reaction time is 0.01-72 h.
10. Use of a hexagonal layered boride ceramic h-MAB material according to any one of claims 1 to 4, characterized in that: the h-MAB phase material is used as a coating material in an extreme working environment and as a precursor of a two-dimensional material.
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| CN115418592A (en) * | 2022-08-01 | 2022-12-02 | 海南大学 | Chloride molten salt corrosion resistant coating and preparation method thereof |
| CN115595543A (en) * | 2022-10-28 | 2023-01-13 | 西安理工大学（Cn） | MoAlB ceramic film with MAB phase structure and preparation method thereof |
| CN116040640A (en) * | 2023-02-21 | 2023-05-02 | 哈尔滨工业大学 | Method for synthesizing MAB phase ceramic powder |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114988425A (en) * | 2022-04-08 | 2022-09-02 | 中国科学院宁波材料技术与工程研究所 | MAX phase material with boron element stable X bit as chalcogen element, preparation method and application thereof |
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| CN115595543A (en) * | 2022-10-28 | 2023-01-13 | 西安理工大学（Cn） | MoAlB ceramic film with MAB phase structure and preparation method thereof |
| CN115595543B (en) * | 2022-10-28 | 2024-06-07 | 西安理工大学 | MoAlB ceramic film with MAB phase structure and preparation method thereof |
| CN116040640A (en) * | 2023-02-21 | 2023-05-02 | 哈尔滨工业大学 | Method for synthesizing MAB phase ceramic powder |
| CN116040640B (en) * | 2023-02-21 | 2024-05-28 | 哈尔滨工业大学 | Method for synthesizing MAB phase ceramic powder |
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