MAX PHASE MATERIAL, PREPARATION METHOD THEREFOR AND APPLICATION THEREOF
20200407281 ยท 2020-12-31
Assignee
- NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES (Ningbo, CN)
Inventors
- Qing HUANG (Ningbo, CN)
- Mian LI (Ningbo, CN)
- Youbing LI (Ningbo, CN)
- Xiaobing ZHOU (Ningbo, CN)
- Kan LUO (Ningbo, CN)
- Shiyu DU (Ningbo, CN)
- Zhengren HUANG (Ningbo, CN)
Cpc classification
C04B2235/3286
CHEMISTRY; METALLURGY
C04B2235/3244
CHEMISTRY; METALLURGY
C04B2235/3256
CHEMISTRY; METALLURGY
C04B2235/3284
CHEMISTRY; METALLURGY
C04B2235/3241
CHEMISTRY; METALLURGY
C04B2235/666
CHEMISTRY; METALLURGY
C04B2235/3293
CHEMISTRY; METALLURGY
C04B2235/3281
CHEMISTRY; METALLURGY
C04B2235/3251
CHEMISTRY; METALLURGY
C01B21/06
CHEMISTRY; METALLURGY
C04B2235/40
CHEMISTRY; METALLURGY
C04B2235/5436
CHEMISTRY; METALLURGY
C04B35/58
CHEMISTRY; METALLURGY
C04B2235/3418
CHEMISTRY; METALLURGY
H01F41/00
ELECTRICITY
C04B2235/3262
CHEMISTRY; METALLURGY
C04B2235/3275
CHEMISTRY; METALLURGY
C04B2235/3232
CHEMISTRY; METALLURGY
C04B35/65
CHEMISTRY; METALLURGY
C04B2235/3217
CHEMISTRY; METALLURGY
C04B2235/3272
CHEMISTRY; METALLURGY
C04B2235/3239
CHEMISTRY; METALLURGY
C04B2235/3279
CHEMISTRY; METALLURGY
International classification
Abstract
The disclosure provides an MAX phase material, a preparation method therefor, and application thereof. The molecular formula of the MAX phase material is represented as M.sub.n+1(A.sub.zA.sub.1z).sub.hX.sub.n, wherein M is selected from group IIIB, IVB, VB or VIB elements, A is selected from element Zn, Cu, Ni, Co, Fe or Mn, A is selected from group IB, IIB, VIII, IVA, VA or VIA elements, X is selected from elements C and/or N, n is 1, 2, 3 or 4, 0<z1, a unit cell of the MAX phase material is formed by alternately stacking M.sub.n+1X.sub.n units and (A.sub.zA.sub.zA.sub.1z).sub.h layers of atoms, and h is the number of layers of the (A.sub.zA.sub.zA.sub.1z) layers of atoms located between the M.sub.n+1X.sub.n unit layers, and h is 1, 2 or 3.
Claims
1. An MAX phase material, wherein a molecular formula of the MAX phase material is represented as M.sub.n+1(A.sub.zA.sub.1z).sub.hX.sub.n, wherein A is selected from Zn, Cu, Ni, Co, Fe or Mn element, M is selected from group IIIB, IVB, VB or VIB elements, A is selected from group IIIA, IVA, VA or VIA elements, X is selected from C and/or N elements, n is 1, 2, 3 or 4, 0<z1, h is a number of (A.sub.zA.sub.1z) layers of atoms located between M.sub.n+1X.sub.n unit layers, and h is 1, 2 or 3.
2. The MAX phase material according to claim 1, wherein the MAX phase material has a hexagonal system structure and a space group of P63/mmc, and a unit cell is formed by alternately stacking M.sub.n+1X.sub.n units and (A.sub.zA.sub.1z).sub.h layers of atoms.
3. The MAX phase material according to claim 1, wherein a unit cell of the MAX phase material is formed by alternately stacking M.sub.n+1X.sub.n units and (A.sub.zA.sub.1z).sub.h layers of atoms.
4. The MAX phase material according to claim 1, wherein M comprises any one or a combination of more than two of Sc, Ti, V, Cr, Zr, Nb, Mo, Hf and Ta.
5. The MAX phase material according to claim 1, wherein X is C.sub.xN.sub.y, wherein (x+y)=1.
6. The MAX phase material according to claim 1, wherein a morphology of the MAX phase material comprises powders, bulks or films.
7. A method of using the MAX phase material according to claim 1, wherein the MAX phase material is used to prepare aerospace thermal structure materials, nuclear energy structure materials, high-temperature electrode materials, frictional wear materials, energy storage materials, catalytic materials and electromagnetic shielding and absorption materials, and magnetic refrigeration or magnetic storage.
8. A preparation method for the MAX phase material according to claim 1, comprising a molten-salt method and/or a discharge plasma sintering method.
9. The preparation method according to claim 8, comprising: mixing a precursor MAX phase material, an A and/or A-containing material and an inorganic salt in a molar ratio of 1:(1.5-3):(3-6) to form a reactant mixture, carrying out a high-temperature reaction on the reactant mixture at 400 C.-1000 C. in an inert atmosphere, subsequently carrying out a posttreatment with the reactant mixture to obtain the MAX phase material, wherein the A is at position A; a molecular formula of the precursor MAX phase material is represented as M.sub.m+1AX.sub.m, wherein M is selected from early transition metal elements in group IIIB, IVB, VB or VIB, A is selected from group IIIA or WA elements, X comprises C and/or N elements, m=1, 2 or 3, and A is Zn, Cu, Ni, Co, Fe or Mn element.
10. The preparation method according to claim 9, wherein the A-containing material comprises any one or a combination of more than two of A-containing alloy, A-containing oxides and A-containing salts; and/or, the A and/or A-containing material is a powder having a particle size of 500 nm-50 m.
11. The preparation method according to claim 9, wherein the posttreatment comprises: after the high-temperature reaction is ended, washing the reactant mixture with deionized water, and then drying at 40 C.-80 C. to obtain the MAX phase material.
12. The preparation method according to claim 9, wherein the precursor MAX phase material is any one or a combination of more than two of powders, bulks and films; and/or, the precursor MAX phase material comprises any one or a combination of more than two of Ti.sub.3AlC.sub.2, Ti.sub.3SiC.sub.2, Ti.sub.2AlC, Ti.sub.2AlN, Ti.sub.4AlN.sub.3, Ti.sub.2GaC, V.sub.2AlC, V.sub.2GaC, Cr.sub.2GaN, Cr.sub.2AlC, Sc.sub.2AlC, Zr.sub.2AlC, Zr.sub.2SnC, Nb.sub.2AlC, Nb.sub.4AlC.sub.3, Mo.sub.2AlC, Mo.sub.2GaN, Hf.sub.2AlC, Hf.sub.2AlN, Ta.sub.3AlC.sub.2 and Ta.sub.4AlC.sub.3.
13. The method according to claim 7, wherein the MAX phase material has a hexagonal system structure and a space group of P63/mmc, and a unit cell is formed by alternately stacking M.sub.n+1X.sub.n units and (A.sub.zA.sub.1z).sub.h layers of atoms.
14. The method according to claim 7, wherein a unit cell of the MAX phase material is formed by alternately stacking M.sub.n+1X.sub.n units and (A.sub.zA.sub.1z).sub.h layers of atoms.
15. The method according to claim 7, wherein M comprises any one or a combination of more than two of Sc, Ti, V, Cr, Zr, Nb, Mo, Hf and Ta.
16. The method according to claim 7, wherein X is C.sub.xN.sub.y, wherein (x+y)=1.
17. The method according to claim 7, wherein a morphology of the MAX phase material comprises powders, bulks or films.
18. The preparation method according to claim 8, wherein the MAX phase material has a hexagonal system structure and a space group of P63/mmc, and a unit cell is formed by alternately stacking M.sub.n+1X.sub.n units and (A.sub.zA.sub.1z).sub.h layers of atoms.
19. The preparation method according to claim 8, wherein a unit cell of the MAX phase material is formed by alternately stacking M.sub.n+1X.sub.n units and (A.sub.zA.sub.1z).sub.h layers of atoms.
20. The preparation method according to claim 8, wherein M comprises any one or a combination of more than two of Sc, Ti, V, Cr, Zr, Nb, Mo, Hf and Ta.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE EMBODIMENTS
[0052] As described above, in view of the defects in the prior art, the inventor of the present application proposes the technical solution of the present application through long-term researches and lots of practices. The technical solution, its implementation process and principle and the like will be described in detail below.
[0053] The embodiment of the present application provides an MAX phase material, wherein the molecular formula of the MAX phase material is represented as M.sub.n+1(A.sub.zA.sub.1z).sub.hX.sub.n, M being selected from group IIIB, IVB, IIB, IVA, or VIA elements, A being selected from group IB, IIB, VIII, IVA, VA or VIA elements, A being selected from Zn, Cu, Mn, Fe, Co or Ni element, X being selected from elements C and/or N, n being 1, 2, 3 or 4, 0<z1, h being the number of layers of the (A.sub.zA.sub.1z) layers of atoms located between the M.sub.n+1X.sub.n unit layers, and h being 1, 2 or 3.
[0054] Further, the MAX phase material has a hexagonal system structure and a space group of P63/mmc, and a unit cell is formed by alternately stacking M.sub.n+1X.sub.n units and (A.sub.zA.sub.1z)h layers of atoms.
[0055] Where, as one aspect of the present application, the involved MAX phase material is a novel MAX phase material, its molecular formula is represented as M.sub.n+1(A.sub.zA.sub.1z).sub.hX.sub.n, wherein A is Zn, Cu, Mu, Fe, Co or Ni element, h is the number of layers of the A layers of atoms located between the M.sub.n+1X.sub.n unit layers, and the unit cell of the MAX phase material is formed by alternately stacking M.sub.n+1X.sub.n units and A.sub.h layers of atoms.
[0056] Where, as one aspect of the present application, the involved MAX phase material is a novel MAX phase material, its molecular formula is represented as M.sub.n+1(A.sub.zA.sub.1z).sub.hX.sub.n, wherein M is selected from any one or a combination of more than two of group IIIB, IVB, VB and VIB elements, A is Zn, Cu, Mn, Fe, Co or Ni element, X is any one or a combination of more than two of elements C and/or N, n is 1, 2, 3 or 4, h is the number of layers of the A layers of atoms located between the M.sub.n+1X.sub.n unit layers, and the unit cell of the MAX phase material is formed by alternately stacking M.sub.n+1X.sub.n units and A.sub.h layers of atoms.
[0057] Further, h is 1, 2 or 3.
[0058] Further, the M can preferably comprise any one or a combination of more than two of Sc, Ti, V, Cr, Zr, Nb, Mo, Hf and Ta.
[0059] Further, the X can preferably be C.sub.xN.sub.y, wherein x+y=1.
[0060] Further, the MAX phase material has a hexagonal crystal system structure and a space group of P63/mmc, the unit cell is formed by alternately stacking M.sub.n+1X.sub.n units and A.sub.h layers of atoms.
[0061] Further, the morphology of the MAX phase material comprises any one or a combination of more than two of powders, bulks or films, but is not limited thereto.
[0062] Another aspect of the present application provides a preparation method for a novel MAX phase material, comprising: [0063] mixing a precursor MAX phase material, an A and/or A-containing material and an inorganic salt in a molar ratio of 1:(1.53):(36), carrying out high-temperature reaction on the obtained mixture at 400 C.1000 C. in an inert atmosphere, subsequently carrying out posttreatment to obtain an MAX phase material with A element at the position A; the molecular formula of the precursor MAX phase material is represented as M.sub.m+1AX.sub.m, wherein M is selected from early transition metal elements in group IIIB, IVB, VB or VIB, A is selected from group IIIA or IVA elements, X comprises C and/or N, m=1, 2 or 3, and A is any one or a combination of more than two of Zn, Cu, Ni, Co, Fe and Mn.
[0064] Further, the precursor MAX phase material comprises any one or a combination of more than two of Ti.sub.3AlC.sub.2, Ti.sub.3SiC.sub.2, Ti.sub.2AlC, Ti.sub.2AlN, Ti.sub.4AlN.sub.3, Ti.sub.2GaC, V.sub.2AlC, V.sub.2GaC, Cr.sub.2GaN, Cr.sub.2AlC, Sc.sub.2AlC, Zr.sub.2AlC, Zr.sub.2SnC, Nb.sub.2AlC, Nb.sub.4AlC.sub.3, Mo.sub.2AlC, Mo.sub.2GaN, Hf.sub.2AlC, Hf.sub.2AlN, Ta.sub.3AlC.sub.2 and Ta.sub.4AlC.sub.3, but is not limited thereto.
[0065] Further, the A-containing material comprises any one or a combination of more than two of ZnO, ZnCl.sub.2, ZnBr.sub.2, ZnSO.sub.4, CuO, CuCl.sub.2, CuBr.sub.2, CuSO.sub.4, FeO, FeCl.sub.2, FeBr.sub.2, FeSO.sub.4, NiO, NiCl.sub.2, NiBr.sub.2, NiSO.sub.4, CoO, CoCl.sub.2, CoBr.sub.2, CoSO.sub.4, MnO, MnCl.sub.2, MnBr.sub.2 and MnSO.sub.4, but is not limited thereto.
[0066] Further, the inorganic salt comprises any one or a combination of more than two of NaF, NaK, NaCl, KCl, NaBr and KBr, but is not limited thereto.
[0067] Further, the precursor MAX phase material is any one or a combination of powders, bulks and films.
[0068] Further, the A and/or A-containing material is powder, and the particle size is 500 nm50 m.
[0069] Further, the inorganic salt is powder, and the particle size is 500 nm1 mm.
[0070] In some embodiments, the posttreatment comprises: after the high-temperature reaction is ended, the obtained reactant is washed with deionized water, and then dried at 60100 C. to obtain the novel MAX phase material.
[0071] Another aspect of the embodiment of the present application also provides use of the novel MAX phase material in the fields of preparation of aerospace thermal structure materials, nuclear energy structure materials, high-temperature electrode materials, frictional wear materials, energy storage materials or the like.
[0072] Where, examples of MAX phase materials with Zn and Cu elements at the position A are seen in example 1-example 11.
[0073] Example 1: in this example, the novel MAX phase material is Ti.sub.3ZnC.sub.2, the precursor MAX phase is Ti.sub.3AlC.sub.2, the Zn-containing material is Zn powder, the inorganic salt is NaCl, and these raw materials are all commercially available. The preparation method of Ti.sub.3ZnC.sub.2 is as follows:
[0074] (1) 5.84 g of NaCl, 6 g of Ti.sub.3AlC.sub.2 having a particle size of 10 m and 3 g of Zn powder having 300 meshes were weighed, and the above materials were ground and mixed to obtain a mixed product.
[0075] (2) The mixture was placed in a corumdum crucible to react in a high-temperature tubular furnace. Reaction conditions were as follows: 800 C., 30 min, and argon protection. After the temperature of the tubular furnace was reduced to room temperature, a reaction product in the crucible was taken.
[0076] (3) The reaction product was washed with deionized water: the reaction product was put in a flask, deionized water was added, the above materials were stirred and ultrasonically washed for 30 min and then subjected to standing for 1 h, and supernatant was discarded. After being washed three times, the reaction product was put into a 80 C. oven and then taken out after 24 h, so as to obtain a solid product.
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[0080] Example 2: in this example, the novel MAX phase material is Ti.sub.2ZnC, the precursor MAX phase is Ti.sub.2GaC, the Zn-containing material is ZnSO.sub.4, the inorganic salt is KCl, and these raw materials are all commercially available. The preparation method of Ti.sub.2ZnC is as follows:
[0081] (1) 7.45 g of KCl, 4 g of Ti.sub.2GaC having a particle size of 10 m and 5.4 g of ZnSO.sub.4 were weighed, and the above materials were ground and mixed to obtain a mixed product.
[0082] (2) The mixture was placed in a corumdum crucible to react in a high-temperature tubular furnace. Reaction conditions were as follows: 700 C., 30 min, and argon protection. After the temperature of the tubular furnace was reduced to room temperature, a reaction product in the crucible was taken.
[0083] (3) The reaction product was washed with deionized water: the reaction product was put in a flask, deionized water was added, the above materials were stirred and ultrasonically washed for 30 min and then subjected to standing for 1 h, and supernatant was discarded. After being washed three times, the reaction product was put into a 80 C. oven and taken out after 24 h, so as to obtain a solid product.
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[0087] Example 3: in this example, the novel MAX phase material is Ti.sub.2ZnN, the precursor MAX phase is Ti.sub.2AlN, the Zn-containing material is Zn powder, the inorganic salt is NaBr, and these raw materials are all commercially available. The preparation method of Ti.sub.2ZnN is as follows:
[0088] (1) 10.3 g of NaBr, 4.2 g of Ti.sub.2AlN powder having a particle size of 20 m and 3 g of Zn powder having 300 meshes were weighed, and the above materials were ground and mixed to obtain a mixed product.
[0089] (2) The mixture was placed in a corumdum crucible to react in a high-temperature tubular furnace. Reaction conditions were as follows: 1100 C., 30 min, and argon protection. After the temperature of the tubular furnace was reduced to room temperature, a reaction product in the crucible was taken.
[0090] (3) The reaction product was washed with deionized water: the reaction product was put in a flask, deionized water was added, the above materials were stirred and ultrasonically washed for 30 min and then subjected to standing for 1 h, and supernatant was discarded. After being washed three times, the reaction product was put into a 80 C. oven and taken out after 24 h, so as to obtain a solid product.
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[0094] Example 4: in this example, the novel MAX phase material is V.sub.2ZnN, the precursor MAX phase is V.sub.2AlC, the Zn-containing material is Zn powder, the inorganic salt is NaCl, and these raw materials are all commercially available. The preparation method of V.sub.2ZnN is as follows:
[0095] (1) 5.84 g of NaCl, 4.34 g of V.sub.2AlC powder having a particle size of 10 m and 3 g of Zn powder having 300 meshes were weighed, and the above materials were ground and mixed to obtain a mixed product.
[0096] (2) The mixture was placed in a corumdum crucible to react in a high-temperature tubular furnace. Reaction conditions were as follows: 800 C., 30 min, and argon protection. After the temperature of the tubular furnace was reduced to room temperature, a reactant in the crucible was taken.
[0097] (3) The reaction product was washed with deionized water: the reaction product was put in a flask, deionized water was added, the above materials were stirred and ultrasonically washed for 30 min and then subjected to standing for 1 h, and supernatant was discarded. After being washed three times, the reaction product was put into a 80 C. oven and taken out after 24 h, so as to obtain a solid product.
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[0099] In addition, the inventor of the present application conducts relevant experiments by replacing corresponding raw materials and process conditions in the foregoing examples 1-4 with other raw materials and process conditions described in this description. Results show that Z element-based MAX phase materials can be obtained.
[0100] Example 5: in this example, the novel ternary layered MAX phase material is Ti.sub.3CuC.sub.2, the precursor is Ti.sub.3AlC.sub.2, the Cu-containing material is Cu powder, the inorganic salt is NaCl, and these raw materials are all commercially available. The preparation method of Ti.sub.3CuC.sub.2 is as follows:
[0101] (1) 5.85 g of NaCl, 6 g of Ti.sub.3AlC.sub.2 powder and 1.2 g of Cu powder having 300 meshes were weighed, and the above materials were ground and mixed to obtain a mixed product.
[0102] (2) The mixture was placed in a corumdum crucible to react in a high-temperature tubular furnace. Reaction conditions were as follows: 900 C., 120 min, and argon protection. After the temperature of the tubular furnace was reduced to room temperature, a reactant in the crucible was taken.
[0103] (3) The reaction product was washed with deionized water: the reaction product was put in a flask, deionized water was added, the above materials were stirred and ultrasonically washed for 30 min and then subjected to standing for 1 h, and supernatant was discarded. After being washed three times, the reaction product was washed with ethanol, and then the washed reactant was put into a 40 C. oven and taken out after 12 h, so as to obtain a solid product.
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[0106] Example 6: in this example, the novel ternary layered MAX phase material is a Ti.sub.3CuC.sub.2 bulk material the precursor MAX phase is Ti.sub.3AlC.sub.2, the Cu-containing material is Cu, and these raw materials are all commercially available. The preparation method of Ti.sub.3CuC.sub.2 is as follows:
[0107] (1) 2 g of Ti.sub.3AlC.sub.2 powder having particle size of 30 m and 2 g of Cu powder were weighed, and the above materials were ground and mixed to obtain a mixed product.
[0108] (2) 2 g of the above powder mixture was weighed and placed in a graphite die and then sintered through SRS. Sintering conditions were as follows: 1100 C., preservation for 60 min, temperature rising rate was 100 C./min, argon protection and the voltage was 30 MPa. After the reaction was ended, a product was taken.
[0109] (3) The graphite paper on the surface of the obtained bulk was removed, the surface of the bulk was polished through abrasive paper having different meshes until the mirror surface was formed, and the polished bulk was dried under the condition of 80 C., and taken after 12 h, so as to obtain the Ti.sub.3CuC.sub.2 bulk material.
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[0112] Example 7: in this example, the novel ternary layered MAX phase material is Ti.sub.2CuN, the precursor is Ti.sub.2AlN, the Cu-containing material is Cu powder, the inorganic salt is KCl, and these raw materials are all commercially available. The preparation method of Ti.sub.2CuN is as follows:
[0113] (1) 7.45 g of KCl, 6 g of Ti.sub.2AlN powder having particle size of 10 m and 2.4 g of Cu powder having 300 meshes were weighed, and the above materials were ground and mixed to obtain a mixed product.
[0114] (2) The above powder mixture placed in a corundum crucible to react in a high-temperature tubular furnace. Reaction conditions were as follows: 600 C., preservation for 420 min, and argon protection. After the temperature of the tubular furnace was reduced to room temperature, a reaction product was taken.
[0115] (3) The reaction product was washed with deionized water and ethanol: the reaction product was placed in a flask, deionzied water was added, the above materials were stirred and ultrasonically washed for 30 min and then subjected to standing for 1 h, and supernatant was discarded. After being washed three times, the reaction product was washed with ethanol and then put into a 60 C. oven, and then taken after 12 h, so as to obtain a power product.
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[0118] Example 8: in this example, the novel ternary layered MAX phase material is Ti.sub.2CuN, the precursor MAX phase material is Ti.sub.2AlN, the Cu-containing material is CuO powder, the inorganic salts are NaCl and KCl, and these raw materials are all commercially available. The preparation method of Ti.sub.2CuN is as follows:
[0119] (1) 4.8 g of NaCl, 6.2 g of KCl, 3 g of Ti.sub.2AlN powder and 3 g of Cu powder having 300 meshes were weighed, and the above materials were ground and mixed to obtain a mixed product.
[0120] (2) The above mixture was placed in a corundum crucible to react in a high-temperature tubular furnace. Reaction conditions were as follows: 1000 C., preservation for 180 min, and argon protection. After the temperature of the tubular furnace was reduced to room temperature, a reaction product in the crucible was taken.
[0121] (3) The reaction product was washed with deionized water and ethanol: the reaction product was placed in a flask, deionzied water was added, the above materials were stirred and ultrasonically washed for 30 min and then subjected to standing for 1 h, and supernatant was discarded. After being washed three times, the reaction product was washed with ethanol and then put into a 60 C. oven, and then taken after 12 h, so as to obtain a power product.
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[0124] Example 9: in this example, the novel ternary layered MAX phase material is Ti.sub.2(Cu.sub.xIn.sub.1x)C, the raw material is Ti.sub.2InC, the inorganic salts are NaBr and KBr, and these raw materials are all commercially available. The preparation method of Ti.sub.2(Cu.sub.xIn.sub.1x)C is as follows:
[0125] (1) 2.4 g of NaBr, 3.1 g of KBr, 2 g of Ti.sub.2InC powder and 1.2 g of Cu powder having 300 meshes were weighed, and the above materials were ground and mixed to obtain a mixed product.
[0126] (2) The above mixture was placed in a corundum crucible to react in a high-temperature tubular furnace. Reaction conditions were as follows: 750 C., preservation for 600 min, and argon protection. After the temperature of the tubular furnace was reduced to room temperature, a reaction product in the crucible was taken.
[0127] (3) The reaction product was washed with deionized water and ethanol: the reaction product was placed in a flask, deionzied water was added, the above materials were stirred and ultrasonically washed for 30 min and then subjected to standing for 1 h, and supernatant was discarded. After being washed three times, the reaction product was washed with ethanol and then put into a 50 C. oven, and then taken after 24 h, so as to obtain a power product.
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[0130] Example 10: in this example, the novel ternary layered MAX phase material is V.sub.2(Cu.sub.xAl.sub.1x)C, the precursor is V.sub.2AlC powder, Cu is Cu powder, the inorganic salts are NaCl and KCl, and these raw materials are all commercially available. The preparation method of V.sub.2(Cu.sub.xAl.sub.1x)C is as follows:
[0131] (1) 3.6 g of NaCl, 4.65 g of KCl, 1 g of V.sub.2AlC powder having 300 meshes and 1.2 g of Cu powder having 300 meshes were weighed, and the above materials were ground and mixed to obtain a mixed product.
[0132] (2) The above mixture was placed in a corundum crucible to react in a high-temperature tubular furnace. Reaction conditions were as follows: 400 C., preservation for 720 min, and argon protection. After the temperature of the tubular furnace was reduced to room temperature, a reaction product in the crucible was taken.
[0133] (3) The reaction product was washed with deionized water and ethanol: the reaction product was placed in a flask, deionzied water was added, the above materials were stirred and ultrasonically washed for 30 min and then subjected to standing for 1 h, and supernatant was discarded. After being washed three times, the reaction product was washed with ethanol and then put into a 88 C. oven, and then taken after 24 h, so as to obtain a power product.
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[0135] Example 11: in this example, the novel ternary layered MAX phase material is Ti.sub.3CuC.sub.2, the precursor material is Ti.sub.3AlC.sub.2, CuO powder having 300 meshes is 1.5 g, the inorganic salts are NaCl and KCl, and these raw materials are all commercially available. The preparation method of Ti.sub.3CuC.sub.2 is as follows:
[0136] (1) 1.2 g of NaCl, 1.55 g of KCl, 6 g of Ti.sub.3CuC.sub.2 powder, 1.5 g of CuO powder having 300 meshes, 1.5 g of Al powder and 0.48 g of carbon powder having 300 meshes were weighed, and the above materials were ground and mixed to obtain a mixed product.
[0137] (2) The above mixture was placed in a corundum crucible to react in a high-temperature tubular furnace. Reaction conditions were as follows: 800 C., preservation for 300 min, and argon protection. After the temperature of the tubular furnace was reduced to room temperature, a reaction product in the crucible was taken.
[0138] (3) The reaction product was washed with deionized water and ethanol: the reaction product was placed in a flask, deionzied water was added, the above materials were stirred and ultrasonically washed for 30 min and then subjected to standing for 1 h, and supernatant was discarded. After being washed three times, the reaction product was washed with ethanol and then put into a 45 C. oven and then taken after 24 h, so as to obtain a power product.
[0139]
[0140] Wherein, examples of ternary layered MAX phase materials with Co, Ni, Fe and Mn elements at the position A refer to example 12-example 18.
[0141] Example 12: in this example, the ternary layered MAX phase material with magnetic elements at the position A is V.sub.2(Sn.sub.zFe.sub.1z)C powder material, the precursor is V.sub.2AlC, a Sn-containing material is Sn powder, and a Fe-containing material is Fe powder. The preparation method of the V.sub.2(Sn.sub.zFe.sub.1z)C powder is as follows:
[0142] (1) 1.2 g of NaCl, 1.5 g of KCl, 2 g of V.sub.2AlC powder, 1.3 g of Sn powder having 300 meshes and 0.56 g of Fe powder having 300 meshes were weighed, and the above materials were ground and mixed to obtain a mixture.
[0143] (2) The above mixture was placed in a corundum crucible to react in a high-temperature tubular furnace. Reaction conditions were as follows: 1300 C., preservation for 300 min, and inert atmosphere protection. After the temperature of the tubular furnace was reduced to room temperature, a reaction product in the crucible was taken.
[0144] (3) The reaction product was washed with deionized water and ethanol: the reaction product was placed in a flask, deionzied water was added, the above materials were stirred and ultrasonically washed for 30 min and then subjected to standing for 1 h, and supernatant was discarded. After being washed three times, the reaction product was washed with ethanol and then put into a 40 C. oven, and then taken after 12 h, so as to obtain a power product.
[0145]
[0146]
[0147] Example 13: in this example, the ternary layered MAX phase material with magnetic elements at the position A is a V.sub.2(Sn.sub.zFe.sub.1z)C powder material, the precursor is V.sub.2AlC, a Sn-containing material is Sn powder, and a Fe-containing material is Fe powder. The preparation method of V.sub.2(Sn.sub.zFe.sub.1z)C is as follows:
[0148] (1) 2.4 g of NaCl, 3.1 g of KCl, 3 g of V.sub.2AlC powder, 1.3 g of Sn powder having 300 meshes and 0.34 g of Fe powder having 300 meshes were weighed, and the above materials were ground and mixed to obtain a mixed product.
[0149] (2) The above mixture was placed in a corundum crucible to react in a high-temperature tubular furnace. Reaction conditions were as follows: 900 C., preservation for 420 min, and inert atmosphere protection. After the temperature of the tubular furnace was reduced to room temperature, a reaction product in the crucible was taken.
[0150] (3) The reaction product was washed with deionized water and ethanol: the reaction product was placed in a flask, deionzied water was added, the above materials were stirred and ultrasonically washed for 30 min and then subjected to standing for 1 h, and supernatant was discarded. After being washed three times, the reaction product was washed with ethanol and then put into a 40 C. oven, and then taken after 12 h, so as to obtain a power product.
[0151]
[0152]
[0153]
[0154] Example 14: in this example, the ternary layered MAX phase material with magnetic elements at the position A is a V.sub.2(Sn.sub.zFe.sub.1z)C bulk material, the precursor is V.sub.2AlC, a Sn-containing material is Sn powder, and a Fe-containing material is Fe powder. The preparation method of the V.sub.2(Sn.sub.zFe.sub.1z)C bulk material is as follows:
[0155] (1) 3 g of V.sub.2AlC powder, 1.3 g of Sn powder having 300 meshes and 1 g of Fe powder having 300 meshes were weighed, and the above materials were ground and mixed to obtain a mixed product.
[0156] (2) The above powder mixture was placed in a graphite die and then sintered through SRS. Sintering conditions were as follows: 1100 C., preservation for 120 min, the temperature rising rate was 100 C./min, argon protection and the voltage was 37 MPa. After the reaction was ended, a reaction product was taken.
[0157] (3) The graphite paper on the surface of the obtained bulk was removed, the surface of the bulk was polished through abrasive paper having different meshes until the mirror surface was formed, the polished bulk was put in a 100 C. oven and taken after 12 h, so as to obtain the bulk material.
[0158]
[0159]
[0160] Example 15: in this example, the ternary layered MAX phase material with magnetic elements at the position A is a V.sub.2(Sn.sub.zFe.sub.1z)C powder material, the precursor is V.sub.2AlC, a Sn-containing material is Sn powder, and a Fe-containing material is Fe powder. The preparation method of the V.sub.2(Sn.sub.zFe.sub.1z)C bulk material is as follows:
[0161] (1) 2.4 g of NaCl, 3.1 g of KCl, 3 g of V.sub.2AlC powder, 1.3 g of Sn powder having 300 meshes and 0.15 g of Fe powder having 300 meshes were weighed, and the above materials were ground and mixed to obtain a mixture.
[0162] (2) The above mixture was placed in a corundum crucible to react in a high-temperature tubular furnace. Reaction conditions were as follows: 700 C., preservation for 720 min, and inert atmosphere protection. After the temperature of the tubular furnace was reduced to room temperature, a reaction product in the crucible was taken.
[0163] (3) The reaction product was washed with deionized water and ethanol: the reaction product was placed in a flask, deionzied water was added, the above materials were stirred and ultrasonically washed for 30 min and then subjected to standing for 1 h, and supernatant was discarded. After being washed three times, the reaction product was washed with ethanol and then put into a 80 C. oven and then taken after 12 h, so as to obtain a solid product.
[0164]
[0165] Example 16: in this example, the ternary layered MAX phase material with magnetic elements at the position A is a V.sub.2(Sn.sub.zCo.sub.1z)C powder material, the precursor is V.sub.2AlC, a Sn-containing material is Sn powder, and a Co-containing material is Co powder. The preparation method of the V.sub.2(Sn.sub.zCo.sub.1z)C block material is as follows:
[0166] (1) Sn powder having 300 meshes, Co powder having 300 meshes, V.sub.2AlC powder and NaCl were weighed, and the above materials were ground and mixed in a molar ratio of 2:1:6:3 to obtain a mixture.
[0167] (2) The above mixture was placed in a corundum crucible to react in a high-temperature tubular furnace. Reaction conditions were as follows: 1200 C., preservation for 100 min, and inert atmosphere protection. After the temperature of the tubular furnace was reduced to room temperature, a reaction product was taken.
[0168] (3) The reaction product was washed with deionized water and ethanol: the reactant was placed in a flask, deionzied water was added, the above materials were stirred and ultrasonically washed for 30 min and then subjected to standing for 1 h, and supernatant was discarded. After being washed three times, the reaction product was washed with ethanol and then s put into a 60 C. oven and then taken after 15 h, so as to obtain a solid product.
[0169] Example 17: in this example, the ternary layered MAX phase material with magnetic elements at the position A is a V.sub.2(Sn.sub.zNi.sub.1z)C powder material, the precursor is V.sub.2AlC, a Sn-containing material is Sn powder, and a Ni-containing material is Ni powder. The preparation method of the V.sub.2(Sn.sub.zNi.sub.1z)C powder material is as follows:
[0170] (1) Sn powder having 300 meshes, Ni powder having 300 meshes, V.sub.2AlC powder and NaCl were weighed, and the above materials were ground and mixed in a molar ratio of 3:1:6:3 to obtain a mixture.
[0171] (2) The above mixture was placed in a corundum crucible to react in a high-temperature tubular furnace. Reaction conditions were as follows: 1000 C., preservation for 200 min, and inert atmosphere protection. After the temperature of the tubular furnace was reduced to room temperature, a reactant was taken.
[0172] (3) The reaction product was washed with deionized water and ethanol: the reactant was placed in a flask, deionzied water was added, the above materials were stirred and ultrasonically washed for 30 min and then subjected to standing for 1 h, and supernatant was discarded. After being washed three times, the reaction product was washed with ethanol and then put into a 80 C. oven, and then taken after 15 h, so as to obtain a solid product.
[0173] Example 18: in this example, the ternary layered MAX phase material with magnetic elements at the position A is a V.sub.2(Sn.sub.zMn.sub.1z)C powder material, the precursor is V.sub.2AlC, a Sn-containing material is Sn powder, and a Ni-containing material is Ni powder. The preparation method of the V.sub.2(Sn.sub.zMn.sub.1z)C powder material is as follows:
[0174] (1) Sn powder having 300 meshes, Mn powder having 300 meshes, V.sub.2AlC powder, NaCl and KCl were weighed, and the above materials were ground and mixed in a molar ratio of 4:1:10:3:3 to obtain a mixture.
[0175] (2) The above mixture was placed in a corundum crucible to react in a high-temperature tubular furnace. Reaction conditions were as follows: 800 C., preservation for 600 min, and inert atmosphere protection. After the temperature of the tubular furnace was reduced to room temperature, a reaction product was taken.
[0176] (3) The reaction product was washed with deionized water and ethanol: the reaction product was placed in a flask, deionzied water was added, the above materials were stirred and ultrasonically washed for 30 min and then subjected to standing for 1 h, and supernatant was discarded. After being washed three times, the reaction product was washed with ethanol and then put into a 50 C. oven, and then taken after 15 h, so as to obtain a solid product.
[0177] The properties of the ternary layered MAX phase material with magnetic elements at the position A obtained in examples 16-18 of the present application are basically consistent with those of the product in examples 12-15.
[0178] In addition, the inventor of the present application conducts relevant experiments by replacing corresponding raw materials and process conditions in the foregoing examples 12-18 with other raw materials and process conditions described in the specification. All the results show that MAX phase materials with Zn, Cu, Mn, Fe, Co, Ni and other elements at the position A can be obtained.
[0179] In summary, compared with the existing MAX phase materials, the novel MAX phase material provided by the forgoing examples of the present application have the advantages of high intensity, high heat conductivity, high electric conductance, oxidization resistance, magnetism, high temperature tolerance, high damage tolerance, machinability and the like, and the preparation process is simple to operate, and has application prospect in the fields of aerospace thermal structural materials, nuclear energy structural materials, energy storage, catalysis, wave absorption, electromagnetic shielding, spin electron, magnetic refrigeration, magnetic storage and the like.
[0180] It should be understood that the above descriptions are only examples of the present application, but therefore limit the patent scope of the present application. Equivalent structures or equivalent flowchart transformations made by utilizing the contents of the Description and drawings of the present application are directly or indirectly applied to the other relevant technical fields, and are all included in the patent protection scope of the present application.