CN112094121A - High-entropy MAX phase solid solution material in sulfur system and preparation method and application thereof - Google Patents

High-entropy MAX phase solid solution material in sulfur system and preparation method and application thereof Download PDF

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CN112094121A
CN112094121A CN202011012192.XA CN202011012192A CN112094121A CN 112094121 A CN112094121 A CN 112094121A CN 202011012192 A CN202011012192 A CN 202011012192A CN 112094121 A CN112094121 A CN 112094121A
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phase solid
sulfur
transition metal
solution material
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黄庆
陈科
周小兵
宋育杰
周洁
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Hangzhou Bay Research Institute Of Ningbo Institute Of Materials
Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention discloses a high-entropy MAX phase solid solution material in a sulfur system, and a preparation method and application thereof. M position of the high-entropy MAX phase solid solution material in the sulfur system comprises any three or more than four combinations of transition metal elements of Ti, Zr, Hf, V, Nb and Ta, A position is sulfur element, and X position is carbon element. The preparation method comprises the following steps: ferrous sulfide is used as a high-temperature solid sulfur source, transition metal sulfide is obtained through a displacement reaction between a transition metal simple substance and the ferrous sulfide, and then the transition metal sulfide reacts with metal carbide to obtain the high-entropy MAX-phase solid solution material in the sulfur system. The ferrous sulfide sulfur source and the sulfur-containing intermediate product adopted by the invention are stable metal sulfides, so that the volatilization of elemental sulfur in the high-temperature preparation process is avoided, and the synthetic path of a target phase is favorably controlled; the obtained high-entropy MAX phase solid solution material in the sulfur system is expected to have good application prospect in the field of extreme environment structure materials such as nuclear power, high-speed rails and the like.

Description

High-entropy MAX phase solid solution material in sulfur system and preparation method and application thereof
Technical Field
The invention relates to a MAX phase solid solution material, in particular to a high-entropy MAX phase solid solution material in a sulfur system, and a preparation method and application thereof, belonging to the technical field of MAX phase materials of ternary layered compounds.
Background
The MAX phase is a nano-layered ternary compound with structure and performance diversity and is in a hexagonal symmetric structure (P6)3/mmc) having Mn+1AXnThe general molecular formula (II) is shown in the specification. Where M is an early transition metal, A is typically a group IIIA or IVA element, X is carbon or nitrogen and n is 1-3 (M.W.Barsum et al, prog.solid State chem., 2000, 28, 201-281). The crystal structure of the MAX phase is generally considered to be formed by Mn+1XnThe nanostructure sub-layers and the A-site monoatomic layer are alternately stacked. Wherein M isn+1XnThe nanostructure sublayer is composed of covalent bonds6X octahedron layer, X element occupies octahedron interval of M element. And A is a monoatomic layer and Mn+1XnThe interaction force between the nanostructure sub-layers is weak and is in a state similar to a metal bond. Two adjacent M in the MAX phase crystal structuren+1XnThe sublayers are twinned and the mirror surfaces are on the sandwiched a-site monoatomic layer (p. eklund et al, Thin Solid Films, 2010, 518, 1851-. Theoretical calculations predict that more than 600 MAX phases are thermodynamically stable, with over 70 pure MAX phases that have been successfully synthesized (s. aryal et al, phys. status Solidi B, 2014, 251, 1480-1497). The M-bit, A-bit and X-bit element distributions of the MAX phases that have been found to date include 14M-bit elements, 17A-bit elements and 2X-bit elements. These MAX phases are generally combined with the lightweight, high strength, oxidation resistance, creep resistance and properties of ceramicsGood thermal stability, as well as high electrical conductivity, high thermal conductivity, relative flexibility and good damage tolerance, high temperature plasticity and processability of metals (m.w. barsum et al, prog.solid State chem., 2000, 28, 201-281); recent studies have also found that MAX phases have low irradiation activity and good material connection properties (c.wang et al, Nature Communications, 2019, 10, 622; x.zhou et al, Carbon, 2016, 102: 106-. Therefore, most of the current research on the corresponding application areas of MAX is mainly focused on the direction of high-safety structural materials including high-temperature electrodes, high-speed pantograph, nuclear fuel cladding tube, and the like.
High-entropy and high-entropy ceramics are one of the current research hotspots. The medium-high entropy ceramic is based on the principle that the Gibbs free energy of a system is reduced by increasing the numerical value of the configuration entropy in a compound, and a ceramic material with high hardness, high strength, good fracture toughness and oxidation resistance is obtained. Generally this configuration entropy can be expressed as
Figure BDA0002695869520000011
Wherein k isBIs the Boltzmann constant, xiIs the mole fraction of the i component. Generally, three different elements are required for the components of the medium-entropy ceramics, and four or more different elements are required for the components of the high-entropy ceramics. At present, high entropy of oxides, carbides, borides, nitrides and silicides has been achieved. The MAX phase has rich chemical diversity, and the MAX phase solid solution with double solid solution can be obtained through M position, A position and X position. The synthesis of (Ti, Zr, Hf, Nb, Ta) has been carried out by researchers2The high entropy MAX phase of AlC, however, the high entropy MAX phase with A as a chalcogenide has not been reported (W.Bao et al, script Mater., 2020, 183, 33-38).
Compared with the conventional MAX phase with the similar A site to the free metal aluminum layer, the sulfur in the MAX phase of the sulfur system has strong bonding force with the M site metal atom. Thus, for the same type of MAX phase, the MAX phase with sulfur in the a-site has a higher young's modulus, shear modulus and hardness. (y.l.du et al, physics.b-Condensed matter, 2010, 405, 720-. The exploration and synthesis of the sulfur-containing medium-high entropy MAX have important significance for further improving the physical and chemical properties of the MAX phase and expanding the application.
Disclosure of Invention
The invention mainly aims to provide a high-entropy MAX phase solid solution material in a sulfur system and a preparation method thereof, so that the defects in the prior art are overcome, and the problems that high temperature required by high-entropy MAX phase synthesis in the sulfur system is volatile and unstable with a simple substance sulfur source, and a target phase with higher purity is difficult to synthesize are solved.
The invention also aims to provide application of the high-entropy MAX phase solid solution material in the sulfur system.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a high-entropy MAX phase solid solution material in a sulfur system, wherein the M site comprises any three (medium entropy) or combination of more than four (high entropy) of transition metal elements Ti, Zr, Hf, V, Nb and Ta, the A site is a sulfur element, and the X site is a carbon element.
In some embodiments, the high-entropy MAX phase solid solution material in the sulfur system has a chemical formula of M2SC, wherein
Figure BDA0002695869520000021
MiComprises any three or more than four of Ti, Zr, Hf, V, Nb and Ta, xiIs MiThe molar constant of the component at the M position, n is 3-5, i refers to the ith component, and the value is an integer from 1 to n.
The embodiment of the invention also provides a preparation method of the high-entropy MAX phase solid solution material in the sulfur system, which comprises the following steps:
providing ferrous sulfide as a high-temperature solid sulfur source;
reacting the mixture containing the ferrous sulfide, the transition metal simple substance and/or the transition metal hydride and the transition metal carbide at 1400-1800 ℃ for 10-30 min to obtain the high-entropy MAX-phase solid solution material in the sulfur system, wherein the chemical formula of the high-entropy MAX-phase solid solution material is M2SC, wherein M comprises any three or four of Ti, Zr, Hf, V, Nb and TaA combination of (a) and (b).
In some embodiments, the preparation method specifically comprises:
mixing ferrous sulfide, transition metal simple substances and/or transition metal hydrides and transition metal carbides according to the molar ratio of (1.0-1.2) to (1.9-2.1) to (0.8-1) to obtain a mixture;
and (3) heating the mixture to 1400-1800 ℃ at a heating rate of 25-50 ℃/min by adopting a spark plasma sintering system, carrying out heat preservation reaction for 10-30 min, and then carrying out post-treatment to obtain the high-entropy MAX phase solid solution material in the sulfur system.
Further, the transition metal simple substance includes any three or a combination of four or more of Ti, Zr, Hf, V, Nb, Ta, and the like, but is not limited thereto.
Further, the transition metal carbide includes any three or a combination of four or more of TiC, ZrC, HfC, VC, NbC, TaC, and the like, but is not limited thereto.
The embodiment of the invention also provides application of the high-entropy MAX phase solid solution material in the sulfur system in the field of preparation of nuclear power, high-speed rail and other extreme environment structure materials.
Compared with the prior art, the invention has the advantages that:
(1) according to the preparation method, the ferrous sulfide is used as a high-temperature solid sulfur source, the transition metal sulfide is obtained through the replacement reaction between the transition metal simple substance and the ferrous sulfide, and then the transition metal sulfide is combined with the metal carbide, so that the ternary, quaternary and quinary MAX-phase solid solution material of the sulfur system is successfully obtained. The method is simple and easy to implement, the sulfur-series multi-component (high-entropy) MAX phase solid solution material with high purity can be obtained by combining the pickling post-treatment process, and the design of the synthetic process of other non-aluminum-series multi-component MAX phase solid solution materials is referred;
(2) the high-entropy MAX-phase solid solution material in the sulfur system obtained by the invention is expected to have good application prospect in the field of extreme environment structure materials such as nuclear power, high-speed rail and the like.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows (Ti, Zr, Hf) prepared in example 1 of the present invention2XRD pattern of entropy MAX phase solid solution material in SC;
FIGS. 2a to 2e show (Ti, Zr, Hf) prepared in example 1 of the present invention2SEM image of entropy MAX phase solid solution material in SC;
FIG. 3 shows (Ti, Zr, Hf, V) prepared in example 2 of the present invention2XRD pattern of SC high entropy MAX phase solid solution material;
FIGS. 4a to 4f are (Ti, Zr, Hf, V) compounds prepared in example 2 of the present invention2SEM image of SC high-entropy MAX phase solid solution material;
FIG. 5 shows (Ti, Zr, Hf, V, Nb) prepared in example 3 of the present invention2XRD pattern of SC high entropy MAX phase solid solution material;
FIGS. 6a to 6g are (Ti, Zr, Hf, V, Nb) compounds prepared in example 3 of the present invention2SEM images of SC high entropy MAX phase solid solution materials.
Detailed Description
In view of the defects of the prior art, the inventors of the present invention have made long-term research and extensive practice to provide a technical solution of the present invention, which mainly uses ferrous sulfide as a high-temperature solid sulfur source, mixes a transition metal simple substance (and/or transition metal hydride) or a metal carbon compound according to a target phase element ratio, and can obtain a high-entropy MAX-phase solid solution material in a sulfur system under a certain temperature condition, and the purity of the MAX-phase can be further improved by acid washing the obtained powder. The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In one aspect of the embodiment of the present invention, M sites of the high-entropy MAX-phase solid solution material in the sulfur system include any three or a combination of four or more of transition metal elements Ti, Zr, Hf, V, Nb, Ta, etc., where a site is a sulfur element and an X site is a carbon element. When the M position consists of three elements, the MAX phase solid solution can meet the definition requirement of the medium entropy ceramic; when the M site is composed of four or more elements, the MAX phase solid solution can meet the definition requirement of the high-entropy ceramic.
In some embodiments, the high-entropy MAX phase solid solution material in the sulfur system has the following chemical formula M2SC, wherein
Figure BDA0002695869520000041
MiComprises any three or more than four of Ti, Zr, Hf, V, Nb and Ta, xiIs MiThe molar constant of the component at the M position, n is 3-5, i refers to the ith component, and the value is an integer from 1 to n (for example, the value is 1, 2 … … n).
In some embodiments, the high-entropy MAX phase solid solution material in the chalcogenide has a hexagonal layered structure with a space group of P63/mmc.
In some embodiments, the particle size distribution of the high-entropy MAX phase solid solution material in the sulfur system is about 1-10 μm.
In some embodiments, the high entropy MAX phase solid solution material in the sulfur system comprises (Ti, Zr, Hf)2SC、(Ti，Zr，V)2SC、(V，Nb，Ta)2SC、(Ti，Zr，Hf，V)2SC、(Ti，Zr，Hf，V，Nb)2SC, etc., or a combination of two or more of them, but not limited thereto.
The preparation method of the high-entropy MAX-phase solid solution material in the sulfur system provided by the embodiment of the invention comprises the following steps: providing ferrous sulfide as a high-temperature solid sulfur source;
reacting the mixture containing the ferrous sulfide, the transition metal simple substance and/or the transition metal hydride and the transition metal carbide at 1400-1800 ℃ for 10-30 min to obtain the high-entropy MAX-phase solid solution material in the sulfur system, wherein the chemical formula of the high-entropy MAX-phase solid solution material is M2SC, wherein M comprises any three or more of Ti, Zr, Hf, V, Nb and Ta.
In some embodiments, the preparation method specifically comprises:
mixing ferrous sulfide, transition metal simple substances and/or transition metal hydrides and transition metal carbides according to the molar ratio of (1.0-1.2) to (1.9-2.1) to (0.8-1) to obtain a mixture;
and (3) heating the mixture to 1400-1800 ℃ at a heating rate of 25-50 ℃/min by adopting a spark plasma sintering system, carrying out heat preservation reaction for 10-30 min, and then carrying out post-treatment to obtain the high-entropy MAX phase solid solution material in the sulfur system. The reaction mechanism of the preparation method of the present invention may be:
firstly, ferrous sulfide is used as a high-temperature solid sulfur source, transition metal sulfide is obtained through a displacement reaction between transition metal elementary substances (or transition metal hydrides) such as titanium, zirconium, hafnium, vanadium, niobium, tantalum and the like and the ferrous sulfide, and the high-temperature solid sulfur source can perform the displacement reaction with the transition metal elementary substances (or transition metal hydrides) to obtain metal sulfide and elementary substance iron without decomposition to generate elementary substance sulfur. The substitution reaction between the transition metal and ferrous sulfide is required to satisfy the requirement that the transition metal has stronger reducibility than iron. Meanwhile, atoms in M-site solid solution need to have smaller atomic radius difference and electronegativity difference; according to the Hume-Rothery semi-empirical rule, the atomic radius difference needs to be less than 8-10%, and the electronegativity difference is less than 0.4-0.5. Furthermore, valence electron solubility and relative valence effects are also considered.
Secondly, the generated metal sulfide and the corresponding metal carbide are subjected to a combination reaction at a certain temperature to obtain a metal carbon sulfur compound, namely, the sulfur series ternary, quaternary and quinary MAX phase solid solution material is successfully obtained.
The ferrous sulfide sulfur source and the sulfur-containing intermediate product adopted by the preparation method are stable metal sulfides, so that the volatilization of elemental sulfur in the high-temperature preparation process is avoided, the control of the synthesis path of a target phase is facilitated, and the pollution of the volatilized sulfur to experimental equipment and the environment is reduced.
In some embodiments, the elemental transition metal includes any three or a combination of four or more of Ti, Zr, Hf, V, Nb, Ta, and the like, but is not limited thereto.
In some embodiments, the transition metal hydride includes a combination of any three or more of titanium hydride, zirconium hydride, hafnium hydride, vanadium hydride, niobium hydride, tantalum hydride, and the like, but is not limited thereto. The invention can also adopt transition metal hydride mainly to replace the original transition metal simple substance, reduce oxide impurities in the reaction product and be beneficial to improving the purity of the target phase.
In some embodiments, the transition metal carbide includes any three or a combination of four or more of TiC, ZrC, HfC, VC, NbC, TaC, and the like, but is not limited thereto.
In some embodiments, the post-processing comprises: and (3) crushing the high-entropy MAX-phase solid solution material in the sulfur system, and grinding the crushed material to 200-500 meshes to obtain the high-entropy MAX-phase solid solution powder material in the sulfur system with uniform particle size distribution.
In some embodiments, the post-processing further comprises: and carrying out acid washing treatment on the high-entropy MAX phase solid solution powder material in the sulfur system. The elementary substance iron remained in the reaction can be removed by an acid washing process so as to improve the purity of the final target phase.
Further, the acid washing treatment comprises: and (3) placing the high-entropy MAX-phase solid solution powder material in the sulfur system in acid liquor with the temperature of room temperature to 100 ℃ and the molar concentration of 1-5 mol/L for etching treatment for 1-3 days.
Further, the acid solution includes hydrochloric acid, sulfuric acid, and the like, but is not limited thereto.
Further, the specific process of the acid washing treatment preferably comprises the following steps: and (3) treating the high-entropy MAX-phase solid solution powder material in the sulfur system after reaction in dilute hydrochloric acid or dilute sulfuric acid with the molar concentration of 1-5 mol/L at the temperature of room temperature-100 ℃ for 1-3 days.
Furthermore, the method is simple and easy to implement, the sulfur system high-entropy MAX phase solid solution material with high purity can be obtained by combining the pickling post-treatment process, and the design of the synthetic process of other non-aluminum system multi-element MAX phase solid solution materials is referred.
The embodiment of the invention also provides application of the high-entropy MAX phase solid solution material in the sulfur system, and the high-entropy MAX phase solid solution material is expected to have good application prospect in the field of extreme environment structure materials such as nuclear power and high-speed rails.
The technical solutions in the present invention are clearly and completely described below with reference to the drawings and the embodiments of the specification, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. It is noted that the materials in the examples below are commercially available or self-prepared, and the experimental equipment and equipment involved are also available from sources known to those skilled in the relevant art.
Example 1:
in this example, the sulfur system intermediate entropy MAX phase solid solution material is (Ti, Zr, Hf)2And (4) SC. The preparation steps of the solid solution material are as follows:
(1) selecting titanium carbide, zirconium carbide, hafnium hydride and ferrous sulfide as raw materials, and adding TiC: zr: ZrC: HfH2: the mol ratio of FeS is 2: 1: 2: 3.2, and the FeS is mixed for 30min by taking alcohol as a medium in grinding and dried in a vacuum drying oven. In this embodiment, if the simple substance of hafnium is easily oxidized, the use of hafnium hydride is advantageous for improving the purity of the target phase.
(2) And (3) adopting a spark plasma sintering system, and keeping the temperature at 1600 ℃ for 20min at the heating rate of 50 ℃/min.
(3) And (3) crushing the powder prepared in the step (2), and grinding the powder to 300 meshes to obtain precursor powder with uniform particle size distribution.
(4) Selecting dilute hydrochloric acid water solution with the concentration of 3mol/L as a corrosive agent, etching for 2 days at 50 ℃, and fully and magnetically stirring. (5) And (3) filtering the product obtained in the step (4) by using a polyvinylidene fluoride microporous filter membrane (PVDF, the aperture is 0.45 mu m) as a separation membrane, fully cleaning the product by using deionized water, cleaning the product by using ethanol, and then drying the product in vacuum at room temperature.
And (4) detecting the powder treated in the step (3) by utilizing X-ray diffraction spectrum (XRD). (R) can be obtained by the Reitveld method full spectrum analysiswp10.2%), which successfully synthesized (Ti, Zr, Hf)2The lattice constant of the solid solution material of the entropy MAX phase in SC (shown in figure 1) is 0.3334nm and 1.1797 nm. The small amount of hafnium oxide impurities and iron in the powder may be derived from the oxidation of hafnium during the preparation process, and the small amount of iron may be derived from the by-product obtained by the substitution reaction of ferrous sulfide and metal raw material.
When the powder treated in step (5) is observed by a Scanning Electron Microscope (SEM), the synthesized powder exhibits a typical MAX phase layered structure (see fig. 2a to 2 d). As shown in Table 1, the above-mentioned presumption can be further verified by energy spectrum analysis, and the powder is composed of Ti, Zr, Hf, S, C, O and other elements, wherein the ratio of the sum of atomic percentages of the Ti, Zr and Hf elements at M position to the atomic percentage of S is 1.98 and is approximately 2, which is in accordance with the experimental design and XRD analysis.
Table 1: the result of energy spectrum analysis of the obtained powder
Figure BDA0002695869520000071
Example 2:
in this example, the sulfur-based high-entropy MAX phase solid solution material is (Ti, Zr, Hf, V)2And (4) SC. The preparation steps of the solid solution material are as follows:
(1) selecting titanium carbide, zirconium, hafnium hydride, vanadium carbide and ferrous sulfide as raw materials, and adding TiC: zr: HfH2: VC: the mol ratio of FeS is 2: 4.2, and the FeS is mixed for 30min by taking alcohol as a medium in grinding and dried in a vacuum drying oven.
(2) And (3) adopting a spark plasma sintering system, and keeping the temperature at 1600 ℃ for 20min at the heating rate of 50 ℃/min.
(3) And (3) crushing the powder prepared in the step (2), and grinding the powder to 300 meshes to obtain precursor powder with uniform particle size distribution.
(4) Selecting dilute hydrochloric acid water solution with the concentration of 3mol/L as a corrosive agent, etching for 2 days at 50 ℃, and fully and magnetically stirring.
(5) And (3) filtering the product obtained in the step (4) by using a polyvinylidene fluoride microporous filter membrane (PVDF, the aperture is 0.45 mu m) as a separation membrane, fully cleaning the product by using deionized water, cleaning the product by using ethanol, and then drying the product in vacuum at room temperature.
And (4) detecting the powder treated in the step (5) by utilizing X-ray diffraction spectrum (XRD). (R) can be obtained by the Reitveld method full spectrum analysiswp13.51%), which successfully synthesized (Ti, Zr, Hf, V)2The lattice constant of the SC high-entropy MAX phase solid solution material (shown in figure 3) is 0.3327nm, and c is 1.1723 nm. The impurities of vanadium titanium carbide and hafnium oxide, which appear in the powder in small amounts, belong to the intermediate product which is not completely reacted, and the impurities belong to the oxidation of hafnium element in the preparation process.
When the powder treated in step (5) was observed with a Scanning Electron Microscope (SEM), it was found that the synthesized powder exhibited a typical MAX phase layered structure (see fig. 4a to 4 f). As shown in Table 2, the above-mentioned presumption was confirmed by the energy spectrum analysis, and the powder contained Ti, Zr, Hf, V at M site, S at A site, and the like. Wherein the ratio of the sum of the mole fractions of the Ti, Zr, Hf and V elements at the M site to the mole fraction of S is approximately 2, and meets the requirements of experimental design and XRD analysis.
Table 2: the result of energy spectrum analysis of the obtained powder
Figure BDA0002695869520000081
Example 3:
in this example, the chalcogenide high-entropy MAX phase solid solution material is (Ti, Zr, Hf, V, Nb)2And (4) SC. The preparation steps of the solid solution material are as follows:
(1) selecting titanium, titanium carbide, zirconium, hafnium hydride, vanadium carbide, niobium carbide and ferrous sulfide as raw materials, and mixing the raw materials according to the weight ratio of Ti: TiC: zr: HfH2：VC: NbC: FeS in the molar ratio of 1: 2: 5.1, mixing with alcohol as medium for 30min during grinding, and drying in vacuum drying oven.
(2) And (3) adopting a spark plasma sintering system, and keeping the temperature at 1600 ℃ for 20min at the heating rate of 50 ℃/min.
(3) And (3) crushing the powder prepared in the step (2), and grinding the powder to 300 meshes to obtain precursor powder with uniform particle size distribution.
(4) Selecting dilute hydrochloric acid water solution with the concentration of 3mol/L as a corrosive agent, etching for 2 days at 50 ℃, and fully and magnetically stirring.
(5) And (3) filtering the product obtained in the step (4) by using a polyvinylidene fluoride microporous filter membrane (PVDF, the aperture is 0.45 mu m) as a separation membrane, fully cleaning the product by using deionized water, cleaning the product by using ethanol, and then drying the product in vacuum at room temperature.
And (4) detecting the powder treated in the step (5) by utilizing X-ray diffraction spectrum (XRD). (R) can be obtained by the Reitveld method full spectrum analysiswp15.67%), which successfully synthesized (Ti, Zr, Hf, V, Nb)2SC solid solution material (as shown in fig. 5) has lattice constants of a 0.3316nm and c 1.1652 nm. Vanadium carbide, niobium titanium carbide and hafnium oxide impurities in the powder, the former two belonging to raw materials and intermediate products which are not completely reacted, the latter belonging to oxidation of hafnium element in the preparation process.
When the powder treated in step (3) was observed with a Scanning Electron Microscope (SEM), it was found that the synthesized powder exhibited a typical MAX phase layered structure (see fig. 6a to 6 g). The above presumption can be further verified by energy spectrum analysis, and the powder consists of elements such as Ti, Zr, Hf, V, Nb, S, C, O, etc., wherein the ratio of the sum of the mole fractions of the elements Ti, Zr, Hf, V, Nb in M position to the mole fraction of S is approximately 2, which accords with experimental design and XRD analysis.
Table 3: the result of energy spectrum analysis of the obtained powder
Figure BDA0002695869520000082
Example 4:
in this example, the sulfur seriesThe intermediate entropy MAX phase solid solution material is (Ti, Zr, Ta)2And (4) SC. The preparation steps of the solid solution material are as follows:
(1) selecting titanium carbide, zirconium carbide, tantalum and ferrous sulfide as raw materials, and adding TiC: zr: ZrC: ta: the mol ratio of FeS is 2: 1: 2: 3.2, and the FeS is mixed for 30min by taking alcohol as a medium in grinding and dried in a vacuum drying oven.
(2) And (3) adopting a spark plasma sintering system, and keeping the temperature at 1800 ℃ for 10min at the heating rate of 25 ℃/min.
(3) And (3) crushing the powder prepared in the step (2), and grinding the powder to 200 meshes to obtain precursor powder with uniform particle size distribution.
(4) Selecting 1mol/L dilute hydrochloric acid aqueous solution as corrosive, etching at 50 deg.C for 2 days, and magnetically stirring.
(5) And (3) filtering the product obtained in the step (4) by using a polyvinylidene fluoride microporous filter membrane (PVDF, the aperture is 0.45 mu m) as a separation membrane, fully cleaning the product by using deionized water, cleaning the product by using ethanol, and then drying the product in vacuum at room temperature.
And (4) detecting the powder treated in the step (3) by utilizing X-ray diffraction spectrum (XRD). The full spectrum analysis by the Reitveld method can be used for obtaining that (Ti, Zr, Ta)2Entropy MAX phase solid solution material in SC.
Example 5
In this example, the sulfur system intermediate entropy MAX phase solid solution material is (Ti, Zr, Ta)2And (4) SC. The preparation steps of the solid solution material are as follows:
(1) selecting titanium carbide, zirconium carbide, tantalum and ferrous sulfide as raw materials, and adding TiC: zr: ZrC: ta: FeS in the molar ratio of 1: 1.1: 0.9: 2: 3.2, mixing with alcohol as medium for 30min during grinding, and drying in vacuum drying oven.
(2) And (3) adopting a spark plasma sintering system, and keeping the temperature at 1400 ℃ for 30min at the heating rate of 40 ℃/min.
(3) And (3) crushing the powder prepared in the step (2), and grinding the powder to 500 meshes to obtain precursor powder with uniform particle size distribution.
(4) Selecting dilute sulphuric acid water solution with concentration of 5mol/L as corrosive, etching at 100 deg.C for 1 day, and stirring with magnetic force.
(5) And (3) filtering the product obtained in the step (4) by using a polyvinylidene fluoride microporous filter membrane (PVDF, the aperture is 0.45 mu m) as a separation membrane, fully cleaning the product by using deionized water, cleaning the product by using ethanol, and then drying the product in vacuum at room temperature.
And (4) detecting the powder treated in the step (3) by utilizing X-ray diffraction spectrum (XRD). The full spectrum analysis by the Reitveld method can be used for obtaining that (Ti, Zr, Ta)2Entropy MAX phase solid solution material in SC.
Example 6
This embodiment is substantially the same as embodiment 1 except that: ferrous sulfide (FeS), transition metal simple substance and transition metal hydride (Zr, HfH)2) The molar ratio of the transition metal carbide (TiC, ZrC) to the transition metal carbide is 1.0: 1.9: 0.9.
Example 7
This embodiment is substantially the same as embodiment 1 except that: ferrous sulfide (FeS), transition metal simple substance and transition metal hydride (Zr, HfH)2) The molar ratio of the transition metal carbide (TiC, ZrC) to the transition metal carbide is 1.2: 2.1: 1.
Comparative example 1
This embodiment is substantially the same as embodiment 1 except that: the molar ratio of ferrous sulfide (FeS), transition metal simple substance (Ti) and transition metal carbide (TiC) is 1: 1. Obtained Ti2The hardness (8GPa) of SC is less than that of (Ti, Zr, Hf) with medium and high entropy2SC(9GPa)、(Ti，Zr，Hf，V)2The hardness of SC (10GPa) shows the strength advantage of the material after medium-high entropy change.
Comparative example 2
This embodiment is substantially the same as embodiment 1 except that: the molar ratio of ferrous sulfide (FeS), transition metal simple substance (Zr) and transition metal carbide (TiC) is 1: 1. Obtained (Ti, Zr)2The hardness of SC (about 8GPa) is less than that of (Ti, Zr, Hf) with medium and high entropy2SC(9GPa)、(Ti，Zr，Hf，V)2The hardness of SC (10GPa) shows the strength advantage of the material after medium-high entropy change.
In summary, the ferrous sulfide sulfur source and the sulfur-containing intermediate product adopted by the preparation method are stable metal sulfides, so that the volatilization of elemental sulfur in the high-temperature preparation process is avoided, the synthesis path of a target phase is favorably controlled, and the pollution of the volatilized sulfur to experimental equipment and environment is reduced. The method is simple and easy to implement, the sulfur system high-entropy MAX phase solid solution material with high purity can be obtained by combining the acid pickling post-treatment process, and the design of the synthetic process of other non-aluminum system multi-element MAX phase solid solution materials is referred; meanwhile, the high-entropy MAX phase solid solution material in the sulfur system obtained by the invention is expected to have good application prospect in the field of extreme environment structure materials such as nuclear power, high-speed rail and the like.
In addition, the inventors of the present invention have conducted relevant experiments by replacing the corresponding raw materials and process conditions in the foregoing examples 1 to 3 with other raw materials and process conditions mentioned in the present specification, and the results all show that a high-entropy MAX phase solid solution material in a sulfur system can be obtained. The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is generally to be understood as open-ended and not limiting.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims (10)

1. A high-entropy MAX phase solid solution material in a sulfur system is characterized in that: m position of the high-entropy MAX phase solid solution material in the sulfur system comprises any three or more than four combinations of transition metal elements of Ti, Zr, Hf, V, Nb and Ta, A position is sulfur element, and X position is carbon element.
2. The high-entropy MAX-phase solid solution material in the sulfur system of claim 1, wherein: the chemical formula of the high-entropy MAX phase solid solution material in the sulfur system is M2SC, wherein
Figure FDA0002695869510000011
MiComprises any three or more than four of Ti, Zr, Hf, V, Nb and Ta, xiIs MiThe molar constant of the component at the M position, n is 3-5, i refers to the ith component, and the value is an integer from 1 to n.
3. The high-entropy MAX-phase solid solution material in the sulfur system of claim 1, wherein: the high-entropy MAX-phase solid solution material in the sulfur system has a hexagonal layered structure, and the space group is P63/mmc;
and/or the particle size of the high-entropy MAX phase solid solution material in the sulfur system is 1-10 μm;
and/or the high-entropy MAX phase solid solution material in the sulfur system comprises (Ti, Zr, Hf)2SC、(Ti，Zr，V)2SC、(V，Nb，Ta)2SC、(Ti，Zr，Hf，V)2SC、(Ti，Zr，Hf，V，Nb)2Any one or a combination of two or more types of SC.
4. A method for preparing a high-entropy MAX-phase solid solution material in the sulfur system defined in any one of claims 1 to 3, comprising:
providing ferrous sulfide as a high-temperature solid sulfur source;
reacting the mixture containing the ferrous sulfide, the transition metal simple substance and/or the transition metal hydride and the transition metal carbide at 1400-1800 ℃ for 10-30 min to obtain the high-entropy MAX-phase solid solution material in the sulfur system, wherein the chemical formula of the high-entropy MAX-phase solid solution material is M2SC, wherein M comprises any three or more of Ti, Zr, Hf, V, Nb and Ta.
5. The preparation method according to claim 4, characterized by specifically comprising:
mixing ferrous sulfide, transition metal simple substances and/or transition metal hydrides and transition metal carbides according to the molar ratio of (1.0-1.2) to (1.9-2.1) to (0.8-1) to obtain a mixture;
and (3) heating the mixture to 1400-1800 ℃ at a heating rate of 25-50 ℃/min by adopting a spark plasma sintering system, carrying out heat preservation reaction for 10-30 min, and then carrying out post-treatment to obtain the high-entropy MAX phase solid solution material in the sulfur system.
6. The production method according to claim 4 or 5, characterized in that: the transition metal simple substance comprises any three or more than four of Ti, Zr, Hf, V, Nb and Ta; and/or the transition metal hydride comprises any three or more of titanium hydride, zirconium hydride, hafnium hydride, vanadium hydride, niobium hydride and tantalum hydride.
7. The production method according to claim 4 or 5, characterized in that: the transition metal carbide comprises any three or more than four of TiC, ZrC, HfC, VC, NbC and TaC.
8. The method of manufacturing according to claim 5, wherein the post-treatment comprises: and (3) crushing the high-entropy MAX-phase solid solution material in the sulfur system, and grinding the crushed material to 200-500 meshes to obtain the high-entropy MAX-phase solid solution powder material in the sulfur system with uniform particle size distribution.
9. The method of manufacturing according to claim 8, wherein the post-processing further comprises: carrying out acid washing treatment on the high-entropy MAX phase solid solution powder material in the sulfur system, preferably, the acid washing treatment comprises the following steps: placing the high-entropy MAX-phase solid solution powder material in an acid solution at room temperature to 100 ℃ and at a molar concentration of 1-5 mol/L for etching treatment for 1-3 days; preferably, the acid solution comprises hydrochloric acid and/or sulfuric acid.
10. Use of the high-entropy MAX-phase solid solution material in the sulfur system of any one of claims 1 to 3 in the field of preparation of nuclear or high-iron structural materials.
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