A micro / nano multi-dimensional composite structure reinforced phase material and an in-situ preparation method thereof

Abstract

The application discloses a kind of micro / nano multidimensional composite structure reinforcing phase materials and in-situ preparation method thereof, belong to electric functional material technical field.The reinforcing phase material has double-layer, multidimensional structure, inner layer is micron MAX phase powder, surface layer is in-situ generated nanometer A element oxide particles.Its preparation steps are: after MAX phase powder is preprocessed by ball milling, uniformly mixed with polymeric agent, dispersing agent and deionized water and is frozen granulation, vacuum freeze-drying, finally by high-temperature oxygen pressurized heat treatment is prepared.The reinforcing phase material prepared in the application has good sphericity, controllable particle size, and exhibits excellent fluidity and filling property during the compounding process with Ag, Cu, Al, Sn and other conductive metal powders.Compared with the metal matrix composite material reinforced by original MAX phase powder, the conductivity is greatly improved, and has good mechanical properties, and has the potential for large-scale application in the field of electric contact, electronic circuit, new energy distribution system, etc.

Description

Technical Field

[0001] This invention relates to the field of electrofunctional materials technology, specifically to an in-situ preparation method of micro / nano multidimensional composite structure reinforced phase materials. Background Technology

[0002] MAX phases, a class of conductive ceramic materials with a layered hexagonal crystal structure, are composed of alternating stacked MX and A layers. MX bonds are predominantly covalent or ionic, while MA bonds are mainly metallic. Benefiting from its unique interlayer structure and mixed valence bond combination, MAX phases exhibit dual properties of both metals and ceramics, possessing excellent electrical and thermal conductivity, machinability, high melting point, oxidation resistance, and corrosion resistance. However, MAX phase ceramic materials are sensitive to synthesis processes and reaction environments, making it difficult to control the particle size of currently prepared MAX phase powders. This hinders their application as reinforcing phase materials in metal-based electrofunctional composites, thus necessitating the development of a high-precision MAX phase particle size control technology. Furthermore, under temperature-induced conditions, the A atom layers in the MAX phase readily undergo interfacial interdiffusion with the Ag, Cu, Al, Sn, and other matrices. While this interfacial behavior significantly improves the mechanical properties of the metal-based composite bulk materials, it significantly degrades the electrical conductivity of the composites, severely impeding the performance improvement and application of MAX phase composite electrofunctional materials in the electronic and electrical fields. Therefore, it is also urgent to optimize the composition and structure of the MAX phase powder to suppress the diffusion of the A atomic layer at the interface with the metal matrix, so as to achieve the dual goals of balancing mechanical and electrical properties.

[0003] Traditional dry and wet ball milling processes are the most common and classic methods for controlling powder particle size in the industry. They primarily utilize the continuous pressure and shear force exerted by the impact of the milling balls to rapidly control the particle size. However, this intense mechanical action leads to numerous problems, including difficulty in controlling powder shape, uneven particle size, and numerous internal and surface defects. For the MAX phase, the MA bonds in its crystal structure are easily broken under external forces. Therefore, controlling the MAX phase particle size through mechanical ball milling easily causes a large amount of alumina (A) to escape and be exposed on the powder surface. This results in the A atom layer being more prone to interfacial diffusion with the metal matrix during preparation, further degrading the electrical conductivity of the composite material. Furthermore, reducing the MAX phase particle size inevitably increases the interfacial area between the small-particle MAX phase powder and the metal matrix, inevitably increasing interfacial defects and intensifying interfacial interdiffusion reactions. This, in turn, simultaneously degrades the mechanical and electrical properties of the composite material, which is extremely detrimental to the application of the MAX phase in metal-based electrofunctional materials. Therefore, the key to promoting the comprehensive improvement of the overall performance of MAX phase-reinforced metal matrix composite bulk materials and meeting industrialization needs lies in how to utilize the structural feature that ball milling easily exposes the A element in the MAX phase to the surface and develop novel MAX phase powder size control technology. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a micro / nano multidimensional composite structure reinforced phase material and its in-situ preparation method. This method effectively restricts the outward diffusion of element A, reduces the deterioration of electrical properties caused by the interdiffusion of element A with the matrix material, and simultaneously achieves a high degree of interface matching between the nanoscale oxides generated in-situ on the surface layer and the micron-scale MAX phase in the inner layer, thereby further improving the overall mechanical properties of the material.

[0005] The present invention is achieved through the following technical solutions.

[0006] This invention provides a micro / nano multidimensional composite reinforced phase material, which has a bilayer, multidimensional structure, with the inner layer being micron-sized MAX phase powder and the surface layer being loaded with in-situ generated nano-sized atom oxide particles.

[0007] The micron-scale MAX phase of the inner layer can be Ti3(Al) 1-x Sn x C2, Cr2(Al) 1-x Sn x C, Ti2(Al) 1- xSn x C, Ta3(Al) 1-x Sn x C2, Ti2(Pb) 1-x Al x C, Ti2(Cd) 1-x Sn x C, Zr2(Al) 1-x Bi x C, Ti2(Al) 1-x Cu x N, Ti3(Al) 1-x Fe x C2, Ti3(Al) 1-x Si x C2, Zr3(Al) 1-x Si x C2, Cr2(Al) 1-x Ge x C, Ti2(Al) 1-x In x One or more of (C).

[0008] The nanoscale alumina oxide loaded on the surface can be one or more of the following: Al2O3 / SnO2, PbO2 / Al2O3, CdO / SnO2, Al2O3 / BiO2, Al2O3 / CuO, Al2O3 / Fe2O3, Al2O3 / SiO2, Al2O3 / GeO2, and Al2O3 / In2O3.

[0009] This invention also provides an in-situ preparation method for the above-mentioned micro / nano multidimensional composite structure reinforced phase material, including the following specific steps:

[0010] S1: The original MAX phase powder is vibrated by a vibratory crusher to initially reduce its particle size to the millimeter level;

[0011] S2: The millimeter-sized MAX phase powder is further reduced to the submicron level by wet ball milling in a planetary ball mill;

[0012] S3: Micron-sized MAX phase powder is continuously reduced in particle size by wet ball milling in a high-speed three-dimensional oscillating ball mill.

[0013] S4: Mix submicron-sized MAX phase powder with polymerizing agent, dispersant and deionized water uniformly to obtain a mixed slurry;

[0014] S5: The above slurry is subjected to liquid nitrogen spray freezing granulation and vacuum freeze drying process to obtain initial spherical MAX phase powder;

[0015] S6: The spherical MAX phase powder is subjected to high-temperature oxygen pressure heat treatment in a tube furnace to finally obtain the novel micro / nano multidimensional composite structure reinforced phase powder.

[0016] Preferably, in step S1, the vibration crushing parameters are: each vibration crushing lasts 5-20 seconds, followed by a pause of 30-60 seconds, repeated 3 times, to obtain millimeter-sized MAX phase powder (particle size 0.5-2 mm).

[0017] Preferably, in step S2, the planetary wet ball milling parameters are: the mass ratio of millimeter-sized MAX phase powder: anhydrous ethanol: zirconium silicate (ZrSiO4) grinding balls is 1: (1~3): (1~5), the ball milling time is 2~5 h, and the drying time is 24 h, thus obtaining micron-sized MAX phase powder (particle size 100~500 μm).

[0018] Preferably, in step S3, the wet ball milling parameters of the high-speed three-dimensional oscillating ball mill are: the mass ratio of micron-sized MAX phase powder: anhydrous ethanol: yttrium-stabilized zirconium oxide (YSZ) grinding balls is 1: (1~3): (1~5), the ball milling time is 1~6h, and the submicron-sized MAX phase powder (particle size 1~10 μm) is obtained after drying for 24h.

[0019] Preferably, in step S4, the submicron-sized MAX phase powder, polymerizer, dispersant, and deionized water are magnetically stirred for 2 hours at a mass ratio (m1 : m2 : m3 : m4 = x : y : z : 1-xyz, x=0.1, y=0.1~0.4, z=0.1~0.5) to obtain a granulated mixed slurry for subsequent liquid nitrogen spray freeze granulation and vacuum freeze-drying processes. The polymerizer is polyethylene glycol (PEG) and poly(2-ethyl-2-oxazoline) (PEO). x The initial spherical MAX phase powder was prepared by mixing polyammonium methacrylate (APMA) and n-octanol (1-Octanol) in a mass ratio of x : (1-x), x=0~1.

[0020] Preferably, in step S5, the slurry is first freeze-dried using a spray freeze-drying granulator with a dual-fluid nozzle diameter of 1.5~2 mm, a slurry flow rate of 400~800 ml / h, and a spray pressure of 100~200 kPa; then, it is freeze-dried under vacuum using a freeze dryer with a vacuum degree of 5 Pa, a cold trap temperature of -80 ℃, and freeze-dried for 24 h to obtain micron-sized spherical MAX phase powder (particle size 20~80 μm).

[0021] Preferably, in step S6, the micron-sized spherical MAX phase powder obtained in step S5 is subjected to high-temperature and pressurized oxygen heat treatment in a tube furnace. The heat treatment temperature is 1000~1300 ℃, the heat treatment time is 0.5~4 h, and the pressure variation range of the chamber is 3~8 MPa. That is, nano-sized alumina oxide particles (particle size 100~900 nm) are prepared in situ on the surface of the micron-sized spherical MAX phase powder, and finally a novel micro / nano multidimensional composite structure reinforced phase is obtained.

[0022] Compared with the prior art, the present invention has the following technical effects:

[0023] 1. This invention employs a three-step ball milling pretreatment of MAX phase powder to gradually expose A-site elements within the MAX phase while preserving its layered structure. The powder is then formulated into a slurry with a polymerizing agent, dispersant, and deionized water. This slurry is followed by freeze granulation, vacuum freeze-drying, and high-temperature oxygen pressure heat treatment to prepare a novel micro / nano multidimensional composite reinforced phase material. The inner micron-sized MAX phase serves as the material's main body, primarily providing mechanical support. The in-situ generated nano-sized A-site oxides on the surface effectively restrict the outward diffusion of A, reducing electrical performance degradation caused by interdiffusion between A and the matrix material. Furthermore, the high interface matching between the in-situ generated nano-sized oxides and the inner micron-sized MAX phase further enhances the overall mechanical properties of the material.

[0024] 2. The reinforcing phase material prepared by the method of this invention has good sphericity and controllable particle size, exhibiting excellent flowability and filling properties. After being composited with conductive metals such as Ag, Cu, Al, and Sn, it exhibits tight interfacial bonding and a uniform microstructure. Compared with traditional MAX phase reinforcing phase materials, it significantly improves conductivity and demonstrates good mechanical properties. The MAX phase reinforcing phase material of this invention has the potential for large-scale application in fields such as electrical contacts, electronic circuits, and new energy power distribution systems. Attached Figure Description

[0025] Figure 1 The images show the overall morphology, size, and surface micromorphology of the novel micro / nano multidimensional composite structure reinforced phase powder prepared in Example 1; where (a) and (b) are the overall SEM images and high-magnification SEM images of the surface of the novel micro / nano multidimensional composite structure reinforced phase powder material, respectively.

[0026] Figure 2 The image shows the effect of the novel micro / nano multidimensional composite structure reinforced phase powder material composite technology of this invention. Detailed Implementation

[0027] The above-mentioned and other technical features and advantages of the present invention will be described in more detail below with reference to the accompanying drawings.

[0028] Example 1

[0029] Ti3(Al) 1-x Sn x C2 raw material powder was crushed using a vibratory crusher with a cycle of 20 seconds of crushing followed by a 60-second pause, repeated three times to obtain Ti3(Al) powder with a median particle size of 0.5 mm. 1-x Sn x C2 powder; the above powder, anhydrous ethanol, and zirconium silicate grinding balls were wet-milled in a planetary ball mill for 3 h with a mass ratio of 1:2:2, and dried for 24 h to obtain Ti3(Al) powder with a median particle size of 250 μm. 1-x Sn x C2 powder; then, the above powder, anhydrous ethanol, and yttrium-stabilized zirconia grinding balls were wet-milled in a high-speed three-dimensional vibrating ball mill for 4 h, and dried for 24 h to obtain Ti3(Al) powder with a median particle size of 3 μm. 1-x Sn x C2 powder; Ti3(Al) pretreated by three-step ball milling 1-x Sn xC2 powder was mixed with polymerizing agent (polyethylene glycol and poly(2-ethyl-2-oxazoline) at a mass ratio of 1:2), dispersant (polyammonium methacrylate and n-octanol at a mass ratio of 1:3), and deionized water at a mass ratio of (m1:m2:m3:m4=1:2:2:5) and magnetically stirred for 2 h to obtain a granulated slurry. The slurry was first freeze-dried using a spray freeze-drying granulator with a 1.5 mm diameter dual-fluid nozzle, a flow rate of 400 ml / h, and a spray pressure of 100 kPa. Then, it was freeze-dried under vacuum at a vacuum degree of 5 Pa and a cold trap temperature of -80 ℃ for 24 h to obtain spherical Ti3(Al) particles with a median particle size of 50 μm. 1-x Sn x C2 powder; the above spherical Ti3(Al) powder was processed in a tube furnace. 1-x Sn x C2 powder was subjected to high-temperature and high-pressure oxygen heat treatment at a temperature of 1000 ℃ for 0.5 h at an internal pressure of 3 MPa, ultimately forming spherical Ti3(Al) powder. 1-x Sn x Al2O3 / SnO2 particles were generated in situ on the surface of C2 powder (the median particle size of Al2O3 / SnO2 particles was 300 nm). Figure 1 The images show the morphology, dimensions, and high-magnification surface SEM images of the novel micro / nano multidimensional composite reinforced phase powder material prepared in this embodiment. Figure 2 The image shows the effect of the composite technology of the novel micro / nano multidimensional composite structure reinforcing phase powder prepared in this embodiment with conductive metal powders such as Ag, Cu, Al, and Sn.

[0030] Example 2

[0031] Cr2(Al) 1-x Sn x The raw material powder was crushed using a vibratory crusher with a 5-second vibration followed by a 30-second pause, repeated three times to obtain Cr2(Al) powder with a median particle size of 2 mm. 1-x Sn x C powder; the above powder, anhydrous ethanol, and zirconium silicate grinding balls were wet-milled in a planetary ball mill at a mass ratio of 1:1:1 for 2 h, and dried for 24 h to obtain Cr2(Al) powder with a median particle size of 500 μm. 1-x Sn x )C powder; then the above powder, anhydrous ethanol, and yttrium-stabilized zirconia grinding balls were wet-milled in a high-speed three-dimensional vibrating ball mill at a mass ratio of 1:1:1 for 1 h, and dried for 24 h to obtain Cr2(Al) powder with a median particle size of 10 μm. 1- x Sn x)C powder; Cr2(Al) powder pretreated by three-step ball milling 1-x Sn x C powder was mixed with polymerizing agent (polyethylene glycol and poly(2-ethyl-2-oxazoline) in a mass ratio of 1:1), dispersant (polyammonium methacrylate and n-octanol in a mass ratio of 1:1), and deionized water in a mass ratio of (m1:m2:m3:m4=1:1:3:5) and magnetically stirred for 2 h to obtain a granulated slurry. The slurry was first freeze-dried using a spray freeze-drying granulator with a 2 mm diameter dual-fluid nozzle, a flow rate of 800 ml / h, and a spray pressure of 200 kPa. Then, it was freeze-dried under vacuum at a vacuum degree of 5 Pa and a cold trap temperature of -80 ℃ for 24 h to obtain spherical Cr2(Al) particles with a median particle size of 80 μm. 1-x Sn x )C powder; the above spherical Cr2(Al) powder was processed in a tube furnace. 1-x Sn x Cr2(Al) powder was subjected to high-temperature and high-pressure oxygen heat treatment at a temperature of 1300 °C for 4 h at an internal pressure of 8 MPa, ultimately forming spherical Cr2(Al) powder. 1-x Sn x Al2O3 / SnO2 particles were generated in situ on the surface of the C powder (the median particle size of Al2O3 / SnO2 particles was 900 nm).

[0032] Example 3

[0033] Ti2(Al) 1-x Sn x The raw material powder was crushed using a vibratory crusher with a cycle of 20 seconds of crushing followed by a 60-second pause, repeated three times to obtain Ti2(Al) powder with a median particle size of 0.5 mm. 1-x Sn x Ti2(Al2O3) powder; the above powder, anhydrous ethanol, and zirconium silicate grinding balls were wet-milled in a planetary ball mill for 5 h with a mass ratio of 1:3:5, and dried for 24 h to obtain Ti2(Al2O3) powder with a median particle size of 100 μm. 1-x Sn x Ti2(Al2O3) powder was then prepared. The powder, anhydrous ethanol, and yttrium-stabilized zirconia grinding balls were then wet-milled for 6 hours using a high-speed three-dimensional vibrating ball mill at a mass ratio of 1:3:5. After drying for 24 hours, Ti2(Al2O3) powder with a median particle size of 1 μm was obtained. 1-x Sn x Ti2(Al) powder; Ti2(Al) powder pretreated by three-step ball milling 1-x Sn xPowder C was mixed with polymerizing agent (polyethylene glycol and poly(2-ethyl-2-oxazoline) at a mass ratio of 1:3), dispersant (polyammonium methacrylate and n-octanol at a mass ratio of 1:3), and deionized water at a mass ratio of (m1:m2:m3:m4=1:1:3:5) and magnetically stirred for 2 h to obtain a granulated slurry. The slurry was first freeze-dried using a spray freeze-drying granulator with a 1.5 mm diameter dual-fluid nozzle, a flow rate of 400 ml / h, and a spray pressure of 100 kPa. Then, it was freeze-dried under vacuum at a vacuum degree of 5 Pa and a cold trap temperature of -80℃ for 24 h to obtain spherical Ti2(Al) particles with a median particle size of 20 μm. 1-x Sn x Ti2(Al) powder; the above spherical Ti2(Al) powder was processed in a tube furnace. 1-x Sn x C powder was subjected to high-temperature and high-pressure oxygen heat treatment at a temperature of 1000 °C for 0.5 h at an internal pressure of 3 MPa, ultimately forming spherical Ti2(Al) powder. 1-x Sn x Al2O3 / SnO2 particles were generated in situ on the surface of C powder (the median particle size of Al2O3 / SnO2 particles was 100 nm).

[0034] Example 4

[0035] Ta3(Al) 1-x Sn x C2 raw material powder was crushed using a vibratory crusher with a cycle of 10 seconds of crushing followed by a 30-second pause, repeated three times to obtain Ta3(Al) powder with a median particle size of 1 mm. 1-x Sn x C2 powder; the above powder, anhydrous ethanol, and zirconium silicate grinding balls were wet-milled in a planetary ball mill for 4 h with a mass ratio of 1:3:4, and dried for 24 h to obtain Ta3(Al) powder with a median particle size of 400 μm. 1-x Sn x C2 powder; then, the above powder, anhydrous ethanol, and yttrium-stabilized zirconia grinding balls were wet-milled for 5 h using a high-speed three-dimensional vibrating ball mill at a mass ratio of 1:3:4, and dried for 24 h to obtain Ta3(Al) with a median particle size of 9 μm. 1-x Sn x C2 powder; Ta3(Al) pretreated by three-step ball milling 1-x Sn xC2 powder was mixed with polymerizing agent (polyethylene glycol and poly(2-ethyl-2-oxazoline) at a mass ratio of 1:2), dispersant (polyammonium methacrylate and n-octanol at a mass ratio of 1:2), and deionized water at a mass ratio of (m1:m2:m3:m4=1:2:2:5) and magnetically stirred for 2 h to obtain a granulated slurry. The slurry was first freeze-dried using a spray freeze-drying granulator with a 1.5 mm diameter dual-fluid nozzle, a flow rate of 600 ml / h, and a spray pressure of 150 kPa. Then, it was freeze-dried under vacuum at a vacuum degree of 5 Pa and a cold trap temperature of -80℃ for 24 h to obtain spherical Ta3(Al) particles with a median particle size of 70 μm. 1-x Sn x C2 powder; the above spherical Ta3(Al) powder was processed in a tube furnace. 1-x Sn x C2 powder was subjected to high-temperature and high-pressure oxygen heat treatment at a temperature of 1200 °C for 3 h, with an internal pressure of 6 MPa, ultimately resulting in spherical Ta3(Al) powder. 1-x Sn x Al2O3 / SnO2 particles were generated in situ on the surface of C2 powder (the median particle size of Al2O3 / SnO2 particles was 200 nm).

[0036] Example 5

[0037] Ti2(Pb) 1-x Al x The raw material powder was crushed using a vibratory crusher with a cycle of 10 seconds of crushing followed by a 40-second pause, repeated three times to obtain Ti2(Pb) with a median particle size of 1.5 mm. 1-x Al x Ti2(Pb) powder; the above powder, anhydrous ethanol, and zirconium silicate grinding balls were wet-milled in a planetary ball mill for 3 h with a mass ratio of 1:3:3, and dried for 24 h to obtain Ti2(Pb) powder with a median particle size of 300 μm. 1-x Al x Ti2(Pb) powder was then prepared. The powder, anhydrous ethanol, and yttrium-stabilized zirconia grinding balls were then wet-milled for 4 hours using a high-speed three-dimensional vibrating ball mill at a mass ratio of 1:2:3. After drying for 24 hours, Ti2(Pb) powder with a median particle size of 6 μm was obtained. 1-x Al x Ti2(Pb) powder; Ti2(Pb) powder pretreated by three-step ball milling 1-x Al xC powder was mixed with polymerizing agent (polyethylene glycol and poly(2-ethyl-2-oxazoline) at a mass ratio of 1:2), dispersant (polyammonium methacrylate and n-octanol at a mass ratio of 1:2), and deionized water at a mass ratio of (m1:m2:m3:m4=1:2:3:5) and magnetically stirred for 2 h to obtain a granulated slurry. The slurry was first freeze-dried using a spray freeze-drying granulator with a 1.5 mm diameter dual-fluid nozzle, a flow rate of 500 ml / h, and a spray pressure of 140 kPa. Then, it was freeze-dried under vacuum at a vacuum degree of 5 Pa and a cold trap temperature of -80℃ for 24 h to obtain spherical Ti2(Pb) particles with a median particle size of 60 μm. 1-x Al x Ti2(Pb) powder; the above spherical Ti2(Pb) powder was processed in a tube furnace. 1-x Al x Ti2(Pb) powder was subjected to high-temperature and high-pressure oxygen heat treatment at a temperature of 1250 °C for 2 h at an internal pressure of 4 MPa, ultimately forming spherical Ti2(Pb) powder. 1-x Al x PbO2 / Al2O3 particles were generated in situ on the surface of C powder (the median particle size of PbO2 / Al2O3 particles was 300 nm).

[0038] Example 6

[0039] Ti2(Cd) 1-x Sn x The raw material powder was crushed using a vibratory crusher with a cycle of 15 seconds of vibration followed by a 40-second pause, repeated three times to obtain Ti2(Cd) powder with a median particle size of 1 mm. 1-x Sn x Ti2(Cd) powder; the above powder, anhydrous ethanol, and zirconium silicate grinding balls were wet-milled in a planetary ball mill for 3 h with a mass ratio of 1:3:3, and dried for 24 h to obtain Ti2(Cd) powder with a median particle size of 200 μm. 1-x Sn x Ti2(Cd) powder; then, the above powder, anhydrous ethanol, and yttrium-stabilized zirconia grinding balls were wet-milled for 3 h using a high-speed three-dimensional vibrating ball mill at a mass ratio of 1:3:3, and dried for 24 h to obtain Ti2(Cd) powder with a median particle size of 5 μm. 1- x Sn x Ti2(Cd) powder; Ti2(Cd) powder pretreated by three-step ball milling 1-x Sn xC powder was mixed with polymerizing agent (polyethylene glycol and poly(2-ethyl-2-oxazoline) at a mass ratio of 1:3), dispersant (polyammonium methacrylate and n-octanol at a mass ratio of 1:2), and deionized water at a mass ratio of (m1:m2:m3:m4=1:1:2:5) and magnetically stirred for 2 h to obtain a granulated slurry. The slurry was first freeze-dried using a spray freeze-drying granulator with a 1.5 mm diameter dual-fluid nozzle, a flow rate of 600 ml / h, and a spray pressure of 160 kPa. Then, it was freeze-dried under vacuum at a vacuum degree of 5 Pa and a cold trap temperature of -80 ℃ for 24 h to obtain spherical Ti2(Cd) particles with a median particle size of 50 μm. 1-x Sn x Ti2(Cd) powder; the above spherical Ti2(Cd) powder was processed in a tube furnace. 1- x Sn x Ti2(Cd) powder was subjected to high-temperature and high-pressure oxygen heat treatment at a temperature of 1150 °C for 2 h at an internal pressure of 5 MPa, ultimately forming spherical Ti2(Cd) powder. 1-x Sn x CdO / SnO2 particles were generated in situ on the surface of C powder (the median particle size of CdO / SnO2 particles was 500 nm).

[0040] Example 7

[0041] Zr2(Al) 1-x Bi x The raw material powder was crushed using a vibratory crusher with a cycle of 15 seconds of crushing followed by a 50-second pause, repeated three times to obtain Zr2(Al) powder with a median particle size of 1 mm. 1-x Bi x Zr2(Al2O3) powder; the above powder, anhydrous ethanol, and zirconium silicate grinding balls were wet-milled in a planetary ball mill for 2 h with a mass ratio of 1:3:2, and dried for 24 h to obtain Zr2(Al2O3) powder with a median particle size of 300 μm. 1-x Bi x Zr2(Al2O3) powder was then mixed with anhydrous ethanol and yttrium-stabilized zirconium oxide grinding balls at a mass ratio of 1:3:2 and wet-milled for 3 h using a high-speed three-dimensional vibrating ball mill. After drying for 24 h, Zr2(Al2O3) powder with a median particle size of 5 μm was obtained. 1-x Bi x Zr2(Al) powder; Zr2(Al) powder pretreated by three-step ball milling 1-x Bi xZr2(Al2O3) powder was mixed with polymerizing agent (polyethylene glycol and poly(2-ethyl-2-oxazoline) at a mass ratio of 1:2), dispersant (polyammonium methacrylate and n-octanol at a mass ratio of 1:3), and deionized water at a mass ratio of (m1:m2:m3:m4=1:3:1:5) and magnetically stirred for 2 h to obtain a granulated slurry. The slurry was first freeze-dried using a spray freeze-drying granulator with a 1.5 mm diameter dual-fluid nozzle, a flow rate of 500 ml / h, and a spray pressure of 180 kPa. Then, it was freeze-dried under vacuum at a vacuum degree of 5 Pa and a cold trap temperature of -80 ℃ for 24 h to obtain spherical Zr2(Al2O3) particles with a median particle size of 40 μm. 1-x Bi x Zr2(Al) powder; the above spherical Zr2(Al) powder was processed in a tube furnace. 1-x Bi x Zr2(Al) powder was subjected to high-temperature and pressurized oxygen heat treatment at a temperature of 1050 °C for 2.5 h at an internal pressure of 6 MPa, ultimately forming spherical Zr2(Al) powder. 1-x Bi x Al2O3 / BiO2 particles were generated in situ on the surface of the C powder (the median particle size of Al2O3 / BiO2 particles was 600 nm).

[0042] Example 8

[0043] Ti2(Al) 1-x Cu x The raw material powder was crushed using a vibratory crusher at a rate of 10 seconds of crushing followed by a 60-second pause, repeated three times to obtain Ti2(Al) powder with a median particle size of 1.5 mm. 1-x Cu x Ti2(Al) powder; the above powder, anhydrous ethanol, and zirconium silicate grinding balls were wet-milled in a planetary ball mill for 3 h with a mass ratio of 1:3:1, and dried for 24 h to obtain Ti2(Al) powder with a median particle size of 200 μm. 1-x Cu x Nitrogen oxide (Ni) powder was then mixed with anhydrous ethanol and yttrium-stabilized zirconia grinding balls at a mass ratio of 1:3:1 using a high-speed three-dimensional vibrating ball mill for 3 hours. After drying for 24 hours, Ti2(Al2O3)2 particles with a median particle size of 3 μm were obtained. 1-x Cu x Ti2(Al) powder; Ti2(Al) powder pretreated by three-step ball milling 1-x Cu xNitrogen powder was mixed with polymerizing agent (polyethylene glycol and poly(2-ethyl-2-oxazoline) at a mass ratio of 1:2), dispersant (polyammonium methacrylate and n-octanol at a mass ratio of 1:3), and deionized water at a mass ratio of (m1:m2:m3:m4=1:2:1:5) and magnetically stirred for 2 h to obtain a granulated slurry. The slurry was first freeze-dried using a spray freeze-drying granulator with a 1.5 mm diameter dual-fluid nozzle, a flow rate of 600 ml / h, and a spray pressure of 140 kPa. Then, it was freeze-dried under vacuum at a vacuum degree of 5 Pa and a cold trap temperature of -80℃ for 24 h to obtain spherical Ti2(Al) particles with a median particle size of 60 μm. 1-x Cu x Nitrogen powder; the above spherical Ti2(Al) powder was processed in a tube furnace. 1-x Cu x Nitrogen powder was subjected to high-temperature and high-pressure oxygen heat treatment at a temperature of 1050 °C for 3.5 h at an internal pressure of 7 MPa, ultimately forming spherical Ti2(Al) powder. 1-x Cu x Al2O3 / CuO particles were generated in situ on the surface of N powder (the median particle size of Al2O3 / CuO particles was 500 nm).

[0044] Example 9

[0045] Ti3(Al) 1-x Fe x C2 raw material powder was crushed using a vibratory crusher with a cycle of 15 seconds of crushing followed by a 60-second pause, repeated three times to obtain Ti3(Al) powder with a median particle size of 1 mm. 1-x Fe x C2 powder; the above powder, anhydrous ethanol, and zirconium silicate grinding balls were wet-milled in a planetary ball mill for 2 h with a mass ratio of 1:2:2, and dried for 24 h to obtain Ti3(Al) powder with a median particle size of 400 μm. 1-x Fe x C2 powder; then, the above powder, anhydrous ethanol, and yttrium-stabilized zirconia grinding balls were wet-milled in a high-speed three-dimensional vibrating ball mill for 4 h, and dried for 24 h to obtain Ti3(Al) powder with a median particle size of 2 μm. 1-x Fe x C2 powder; Ti3(Al) pretreated by three-step ball milling 1-x Fe xC2 powder was mixed with polymerizing agent (polyethylene glycol and poly(2-ethyl-2-oxazoline) at a mass ratio of 1:3), dispersant (polyammonium methacrylate and n-octanol at a mass ratio of 1:4), and deionized water at a mass ratio of (m1:m2:m3:m4=1:1:3:5) and magnetically stirred for 2 h to obtain a granulated slurry. The slurry was first freeze-dried using a spray freeze-drying granulator with a 1.5 mm diameter dual-fluid nozzle, a flow rate of 700 ml / h, and a spray pressure of 180 kPa. Then, it was freeze-dried under vacuum at a vacuum degree of 5 Pa and a cold trap temperature of -80℃ for 24 h to obtain spherical Ti3(Al) particles with a median particle size of 70 μm. 1-x Fe x C2 powder; the above spherical Ti3(Al) powder was processed in a tube furnace. 1-x Fe x C2 powder was subjected to high-temperature and high-pressure oxygen heat treatment at a temperature of 1250 °C for 3 h, with an internal pressure of 8 MPa. The final product was obtained in spherical Ti3(Al) powder. 1-x Fe x Al2O3 / Fe2O3 particles were generated in situ on the surface of C2 powder (the median particle size of Al2O3 / Fe2O3 particles was 400 nm).

[0046] Example 10

[0047] Ti3(Al) 1-x Si x C2 raw material powder was crushed using a vibratory crusher with a cycle of 20 seconds of crushing followed by a 60-second pause, repeated three times to obtain Ti3(Al) powder with a median particle size of 0.5 mm. 1-x Si x C2 powder; the above powder, anhydrous ethanol, and zirconium silicate grinding balls were wet-milled in a planetary ball mill for 2 h with a mass ratio of 1:3:3, and dried for 24 h to obtain Ti3(Al) powder with a median particle size of 300 μm. 1-x Si x C2 powder; then, the above powder, anhydrous ethanol, and yttrium-stabilized zirconia grinding balls were wet-milled in a high-speed three-dimensional vibrating ball mill for 2 h with a mass ratio of 1:3:4, and dried for 24 h to obtain Ti3(Al) powder with a median particle size of 6 μm. 1-x Si x C2 powder; Ti3(Al) pretreated by three-step ball milling 1-x Si xC2 powder was mixed with polymerizing agent (polyethylene glycol and poly(2-ethyl-2-oxazoline) at a mass ratio of 1:2), dispersant (polyammonium methacrylate and n-octanol at a mass ratio of 1:3), and deionized water at a mass ratio of (m1:m2:m3:m4=1:2:1:5) and magnetically stirred for 2 h to obtain a granulated slurry. The slurry was first freeze-dried using a spray freeze-drying granulator with a 1.5 mm diameter dual-fluid nozzle, a flow rate of 600 ml / h, and a spray pressure of 200 kPa. Then, it was freeze-dried under vacuum at a vacuum degree of 5 Pa and a cold trap temperature of -80 ℃ for 24 h to obtain spherical Ti3(Al) particles with a median particle size of 60 μm. 1-x Si x C2 powder; the above spherical Ti3(Al) powder was processed in a tube furnace. 1-x Si x C2 powder was subjected to high-temperature and high-pressure oxygen heat treatment at a temperature of 1150 °C for 3.5 h at an internal pressure of 4 MPa, ultimately forming spherical Ti3(Al) powder. 1-x Si x Al2O3 / SiO2 particles were generated in situ on the surface of C2 powder (the median particle size of Al2O3 / SiO2 particles was 300 nm).

[0048] Example 11

[0049] Ti2(Al) 1-x In x The raw material powder was crushed using a vibratory crusher with a cycle of 20 seconds of crushing followed by a 40-second pause, repeated three times to obtain Ti2(Al) powder with a median particle size of 1 mm. 1-x In x Ti2(Al2O3) powder; the above powder, anhydrous ethanol, and zirconium silicate grinding balls were wet-milled in a planetary ball mill for 4 h with a mass ratio of 1:3:4, and dried for 24 h to obtain Ti2(Al2O3) powder with a median particle size of 200 μm. 1-x In x The powder, anhydrous ethanol, and yttrium-stabilized zirconia grinding balls were then wet-milled for 5 h using a high-speed three-dimensional vibrating ball mill at a mass ratio of 1:3:5. After drying for 24 h, Ti2(Al2O3)2 with a median particle size of 4 μm was obtained. 1- x In x Ti2(Al) powder; Ti2(Al) powder pretreated by three-step ball milling 1-x In xPowder C was mixed with polymerizing agent (polyethylene glycol and poly(2-ethyl-2-oxazoline) at a mass ratio of 1:2), dispersant (polyammonium methacrylate and n-octanol at a mass ratio of 1:4), and deionized water at a mass ratio of (m1:m2:m3:m4=1:2:4:5) and magnetically stirred for 2 h to obtain a granulated slurry. The slurry was first freeze-dried using a spray freeze-drying granulator with a 1.5 mm diameter dual-fluid nozzle, a flow rate of 600 ml / h, and a spray pressure of 200 kPa. Then, it was freeze-dried under vacuum at a vacuum degree of 5 Pa and a cold trap temperature of -80 ℃ for 24 h to obtain spherical Ti2(Al) particles with a median particle size of 70 μm. 1-x In x Ti2(Al) powder; the above spherical Ti2(Al) powder was processed in a tube furnace. 1- x In x C powder was subjected to high-temperature and high-pressure oxygen heat treatment at a temperature of 1200 °C for 2.5 h at an internal pressure of 6 MPa, ultimately forming spherical Ti2(Al) powder. 1-x In x Al2O3 / In2O3 particles were generated in situ on the surface of C powder (the median particle size of Al2O3 / In2O3 particles was 600 nm).

[0050] The Ti3(Al) prepared in Example 1 1-x Sn x C2 / (Al2O3 / SnO2) and Ag powder were wet-mixed at a mass ratio of 1:9 for 30 min, dried for 8 h, and then placed into a mold for warm pressing (550 MPa, 120 ℃ / 5 min). After heat treatment at 800 ℃ for 2 h under Ar atmosphere, Ag-based Ti3(Al2O3 / SnO2) was obtained. 1-x Sn x C2 / (Al2O3 / SnO2) composite material.

[0051] The Cr2(Al) prepared in Example 2 1-x Sn x C / (Al2O3 / SnO2) and Cu powder were wet-mixed at a mass ratio of 1:9 for 30 min, dried for 8 h, and then placed into a mold for warm pressing (550 MPa, 120 ℃ / 5 min). After heat treatment at 800 ℃ for 2 h under Ar atmosphere, Cu-based Cr2(Al2O3 / SnO2) powder was obtained. 1-x Sn x )C / (Al2O3 / SnO2) composite material.

[0052] The Ti2(Al) prepared in Example 3 1-x Sn xAl2O3 / SnO2 and Al powder were wet-mixed at a mass ratio of 1:9 for 30 min, dried for 8 h, and then placed into a mold for warm pressing (550 MPa, 120 ℃ / 5 min). After heat treatment at 800 ℃ for 2 h under Ar atmosphere, Al-based Ti2(Al2O3 / SnO2) was obtained. 1-x Sn x )C / (Al2O3 / SnO2) composite material.

[0053] The Ta3(Al) prepared in Example 4 1-x Sn x C2 / (Al2O3 / SnO2) and Sn powder were wet-mixed at a mass ratio of 1:9 for 30 min, dried for 8 h, and then placed into a mold for warm pressing (550 MPa, 120 ℃ / 5 min). After heat treatment at 800 ℃ for 2 h under Ar atmosphere, Sn-based Ta3(Al2O3 / SnO2) was obtained. 1-x Sn x C2 / (Al2O3 / SnO2) composite material.

[0054] The Ti2(Pb) prepared in Example 5 1-x Al x C / (PbO2 / Al2O3) and Ag powder were wet-mixed at a mass ratio of 1:9 for 30 min, dried for 8 h, and then placed into a mold for warm pressing (550 MPa, 120 ℃ / 5 min). After heat treatment at 800 ℃ for 2 h under Ar atmosphere, Ag-based Ti2(PbO2 / Al2O3) was obtained. 1-x Al x )C / (PbO2 / Al2O3) composite material.

[0055] The Ti2(Cd) prepared in Example 6 1-x Sn x C / (CdO / SnO2) and Ag powder were wet-mixed at a mass ratio of 1:9 for 30 min, dried for 8 h, and then placed into a mold for warm pressing (550 MPa, 120 ℃ / 5 min). After heat treatment at 800 ℃ for 2 h under Ar atmosphere, Ag-based Ti2(CdO / SnO2) was obtained. 1-x Sn x C / (CdO / SnO2) composite material.

[0056] The Zr2(Al) prepared in Example 7 1-x Bi x C / (Al2O3 / BiO2) and Ag powder were wet-mixed at a mass ratio of 1:9 for 30 min, dried for 8 h, and then placed into a mold for warm pressing (550 MPa, 120 ℃ / 5 min). After heat treatment at 800 ℃ for 2 h under Ar atmosphere, Ag-based Zr2(Al2O3 / BiO2) was obtained.1-x Bi x C / (Al2O3 / BiO2) composite material.

[0057] The Ti2(Al) prepared in Example 8 1-x Cu x N / (Al2O3 / CuO) and Ag powder were wet-mixed at a mass ratio of 1:9 for 30 min, dried for 8 h, and then placed into a mold for warm pressing (550 MPa, 120 ℃ / 5 min). After heat treatment at 800 ℃ for 2 h under Ar atmosphere, Ag-based Ti2(Al2O3 / CuO) was obtained. 1-x Cu x )N / (Al2O3 / CuO) composite material.

[0058] The Ti3(Al) prepared in Example 9 1-x Fe x C2 / (Al2O3 / Fe2O3) and Ag powder were wet-mixed at a mass ratio of 1:9 for 30 min, dried for 8 h, and then placed into a mold for warm pressing (550 MPa, 120 ℃ / 5 min). After heat treatment at 800 ℃ for 2 h under Ar atmosphere, Ag-based Ti3(Al2O3 / Fe2O3) was obtained. 1-x Fe x C2 / (Al2O3 / Fe2O3) composite material.

[0059] The Ti3(Al) prepared in Example 10 1-x Si x C2 / (Al2O3 / SiO2) and Ag powder were wet-mixed at a mass ratio of 1:9 for 30 min, dried for 8 h, and then placed into a mold for warm pressing (550 MPa, 120 ℃ / 5 min). After heat treatment at 800 ℃ for 2 h under Ar atmosphere, Ag-based Ti3(Al2O3 / SiO2) was obtained. 1-x Si x C2 / (Al2O3 / SiO2) composite material.

[0060] The Ti2(Al) prepared in Example 11 1-x In x C / (Al2O3 / In2O3) and Ag powder were wet-mixed at a mass ratio of 1:9 for 30 min, dried for 8 h, and then placed into a mold for warm pressing (550 MPa, 120 ℃ / 5 min). After heat treatment at 800 ℃ for 2 h under Ar atmosphere, Ag-based Ti2(Al2O3 / In2O3) was obtained. 1-x In x )C / (Al2O3 / In2O3) composite material.

[0061] Comparative Example 1

[0062] Ti3AlC2 and Ag powder were wet-mixed at a mass ratio of 1:9 for 30 min, dried for 8 h, and then placed into a mold for warm pressing (550 MPa, 120 ℃ / 5 min). After heat treatment at 800 ℃ for 2 h under Ar atmosphere, Ag-based Ti3AlC2 composite material was obtained.

[0063] Comparative Example 2

[0064] Cr2AlC and Cu powder were wet-mixed at a mass ratio of 1:9 for 30 min, dried for 8 h, and then placed into a mold for warm pressing (550 MPa, 120 ℃ / 5 min). After heat treatment at 800 ℃ for 2 h under Ar atmosphere, Cu-based Cr2AlC composite material was obtained.

[0065] Comparative Example 3

[0066] Ti2AlC and Al powder were wet-mixed at a mass ratio of 1:9 for 30 min, dried for 8 h, and then placed into a mold for warm pressing (550 MPa, 120 ℃ / 5 min). After heat treatment at 800 ℃ for 2 h in an Ar atmosphere, Al-based Ti2AlC composite material was obtained.

[0067] Comparative Example 4

[0068] Ta3AlC2 and Sn powder were wet-mixed at a mass ratio of 1:9 for 30 min, dried for 8 h, and then placed into a mold for warm pressing (550 MPa, 120 ℃ / 5 min). After heat treatment at 800 ℃ for 2 h under Ar atmosphere, Sn-based Ta3AlC2 composite material was obtained.

[0069] The performance of the composite material prepared above was tested according to GB / T 5586-2016 Basic Performance Test Methods for Electrical Contact Materials, and compared with commercial electrical contact materials. The performance data are shown in Table 1.

[0070] Table 1. Performance data of electrical contact materials

[0071]

[0072] Table 1 shows that the micro / nano multidimensional composite reinforced phase material prepared in this invention exhibits significantly improved conductivity compared to metal matrix composites reinforced with the original MAX phase powder and commercial metal matrix composites. Furthermore, it possesses excellent mechanical properties and has the potential for large-scale application in fields such as electrical contacts, electronic circuits, and new energy power distribution systems. The above description is merely a preferred embodiment of the present invention and is illustrative rather than restrictive. Those skilled in the art will understand that many changes, modifications, and even equivalents can be made within the spirit and scope defined by the claims of this invention, all of which will fall within the protection scope of this invention.

Claims

1. A micro / nano multidimensional composite structure reinforced phase material, characterized in that, The material has a bilayer, multidimensional structure, with the inner layer being micron-sized MAX phase powder and the outer layer being loaded with in-situ generated nano-sized A element oxide particles. The micron-scale MAX phase in the inner layer of the composite reinforcing phase material can be Ti3(Al) 1-x Sn x C2, Cr2(Al) 1-x Sn x C, Ti2(Al) 1-x Sn x C, Ta3(Al) 1-x Sn x C2, Ti2(Pb) 1-x Al x C, Ti2(Cd) 1-x Sn x C, Zr2(Al) 1-x Bi x C, Ti2(Al) 1-x Cu x N, Ti3(Al) 1-x Fe x C2, Ti3(Al) 1-x Si x C2, Zr3(Al) 1-x Si x C2, Cr2(Al) 1-x Ge x C, Ti2(Al) 1-x In x One or more of C; The nanoscale alumina oxide particles loaded on the surface of the composite reinforcing phase material can be one or more of Al2O3 / SnO2, PbO2 / Al2O3, CdO / SnO2, Al2O3 / BiO2, Al2O3 / CuO, Al2O3 / Fe2O3, Al2O3 / SiO2, Al2O3 / GeO2, and Al2O3 / In2O3. The in-situ preparation method of the micro / nano multidimensional composite structure reinforced phase material includes the following specific steps: S1: The original MAX phase powder is crushed by a vibratory crusher to initially reduce its particle size to the millimeter level; S2: The millimeter-sized MAX phase powder is further reduced to the micrometer level by wet ball milling in a planetary ball mill; S3: Micron-sized MAX phase powder is wet-milled using a high-speed three-dimensional oscillating ball mill to continuously reduce its particle size to the submicron level; S4: Mix submicron-sized MAX phase powder with polymerizing agent, dispersant and deionized water uniformly to obtain a mixed slurry; S5: The above mixed slurry is subjected to liquid nitrogen spray freeze granulation and vacuum freeze drying process to obtain initial spherical MAX phase powder; S6: The spherical MAX phase powder is subjected to high-temperature oxygen pressure heat treatment in a tube furnace to obtain the target product: micro / nano multidimensional composite structure reinforced phase powder; The polymerizing agent is polyethylene glycol and poly(2-ethyl-2-oxazoline) in a mass ratio of [missing information]. x : (1- x Preparation, including: x = 0~1, x is neither 0 nor 1; The dispersant is composed of ammonium polymethacrylate and n-octyl alcohol in a mass ratio of [missing information]. x : (1- x Preparation, including: x = 0~1, x is neither 0 nor 1; The mass ratio of the submicron-sized MAX phase powder to the polymerizer, dispersant, and deionized water is: x : y : z : 1- x - y - z ;in: x =0.1, y =0.1~0.4, z =0.1~0.5, 1- x - y - z Not zero.

2. The in-situ preparation method of the micro / nano multidimensional composite structure reinforced phase material as described in claim 1, characterized in that... The specific steps include the following: S1: The original MAX phase powder is crushed by a vibratory crusher to initially reduce its particle size to the millimeter level; S2: The millimeter-sized MAX phase powder is further reduced to the micrometer level by wet ball milling in a planetary ball mill; S3: Micron-sized MAX phase powder is wet-milled using a high-speed three-dimensional oscillating ball mill to continuously reduce its particle size to the submicron level; S4: Mix submicron-sized MAX phase powder with polymerizing agent, dispersant and deionized water uniformly to obtain a mixed slurry; S5: The above mixed slurry is subjected to liquid nitrogen spray freeze granulation and vacuum freeze drying process to obtain initial spherical MAX phase powder; S6: The target product is obtained by subjecting spherical MAX phase powder to high-temperature oxygen pressure heat treatment in a tube furnace. Micro / nano multidimensional composite structure reinforced phase powder.

3. The in-situ preparation method of the micro / nano multidimensional composite structure reinforced phase material as described in claim 2, characterized in that, In step S1, the vibration crushing parameters are: each vibration crushing cycle lasts 5-20 seconds, followed by a pause of 30-60 seconds, repeated 3 times.

4. The in-situ preparation method of the micro / nano multidimensional composite structure reinforced phase material as described in claim 2, characterized in that, In step S2, the planetary wet ball milling parameters are: the mass ratio of millimeter-scale MAX phase powder: anhydrous ethanol: zirconium silicate grinding balls is 1: (1~3): (1~5), the ball milling time is 2~5 h, and the drying time is 24 h.

5. The in-situ preparation method of the micro / nano multidimensional composite structure reinforced phase material as described in claim 2, characterized in that, In step S3, the wet ball milling parameters of the high-speed three-dimensional oscillating ball mill are as follows: the mass ratio of micron-sized MAX phase powder: anhydrous ethanol: yttrium-stabilized zirconia grinding balls is 1: (1~3): (1~5), the ball milling time is 1~6 h, and the drying time is 24 h.

6. The in-situ preparation method of the micro / nano multidimensional composite structure reinforced phase material as described in claim 2, characterized in that, In step S4, submicron-sized MAX phase powder is magnetically stirred with polymerizing agent, dispersant and deionized water for 2 h to obtain granulated mixed slurry for subsequent liquid nitrogen spray freeze granulation and vacuum freeze drying processes.

7. The in-situ preparation method of the micro / nano multidimensional composite structure reinforced phase material as described in claim 2, characterized in that, In step S5, the slurry is first freeze-dried using a spray freeze-drying granulator with a diameter of 1.5~2 mm for the dual-fluid nozzle, a slurry flow rate of 400~800 ml / h, and a spray pressure of 100~200 kPa. Then, it is freeze-dried under vacuum using a freeze dryer with a vacuum degree of 5 Pa, a cold trap temperature of -80 ℃, and a freeze-drying time of 24 h.

8. The in-situ preparation method of the micro / nano multidimensional composite structure reinforced phase material as described in claim 2, characterized in that, In step S6, the micron-sized spherical MAX phase powder obtained in step S5 is subjected to high-temperature and pressurized oxygen heat treatment in a tube furnace. The heat treatment temperature is 1000~1300 ℃, the heat treatment time is 0.5~4 h, and the pressure variation range inside the furnace is 3~8 MPa.

Images