CN111036913A - Pre-alloyed 3D formed high-entropy alloy porous material and preparation method thereof - Google Patents
Pre-alloyed 3D formed high-entropy alloy porous material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a pre-alloyed 3D formed high-entropy alloy porous material and a preparation method thereof, wherein the pre-alloyed 3D formed high-entropy alloy porous material comprises CrMoNbTaV, the porous material adopts high-entropy alloy powder as a raw material, a three-dimensional grid structure as a frame, and a porous sintered body sintered by the high-entropy alloy powder is nested inside the porous material. The high-entropy alloy powder produced by the atomization method has uniform chemical components and fine crystals, and provides a high-quality powder raw material for preparing a high-performance porous filtering material by the following powder metallurgy; the prepared porous material has good physical and chemical stability and good corrosion resistance, and provides stable guarantee for subsequent filtration. The method has the advantages of high porosity, large specific surface area, large-scale sintering time shortening, high corrosion resistance, high oxidation resistance, high chemical stability, high mechanical strength, difficult corrosion, simple and environment-friendly process and batch production.
Description
Technical Field
The invention relates to the technical field of porous materials, in particular to a pre-alloyed 3D formed high-entropy alloy porous material and a preparation method thereof.
Background
The porous material has the advantages of small density, large specific surface area, good air permeability, large adsorption capacity and the like, and is widely applied to the processes of filtration, noise reduction, heat insulation, catalysis and the like in the industries of petrifaction, metallurgy, medicine, environmental protection, machinery and the like.
Since the industrial revolution, especially the metal porous material has been favored. The metal porous material is mainly used for liquid-solid separation, gas-solid separation, damping, sound absorption, heat dissipation, energy absorption, electromagnetic shielding, flame retardance, filtration and other functions, so that the porous material has wide application value in the fields of electrolytic hydrogen evolution, filtration, separation, surface combustion, vibration and noise reduction, phase change heat exchange and the like, and the design of the pore structure enables the metal porous structure to better meet the use requirement and is a constant topic in the field of metal porous materials.
The pore-forming mechanism of the traditional porous material mostly adopts methods such as a reaction pore-forming method and a self-propagating reaction synthesis method, the pore-forming mechanisms of the porous materials prepared by different methods are greatly different, the defects of long pore-forming reaction time, difficult reaction control, easy pore collapse, insufficient strength, poor corrosion resistance, difficult porosity control and the like are comprehensively considered, the pore diameter and the macroscopic morphology are difficult to control, the pores of the porous material prepared by the traditional preparation method are formed by stacking gaps of original powder and gaps in the pore-forming agent removing process, and the environment and samples are polluted by the removal of the pore-forming agent in the preparation process. Greatly limiting the further widening of the application range.
Research finds that the high-entropy alloy has the characteristics of higher entropy value and difficult diffusion of atoms, so that a solid solution phase and a nano structure with high thermal stability, even an amorphous structure, can be easily obtained, the multi-principal-element high-entropy alloy breaks through a traditional alloy design mode based on one alloy element, can be optimally designed through alloy components to obtain an alloy with the excellent performance combination of microstructure simplification, nano precipitates, an amorphous structure, nano crystal grains and the like, high strength, high hardness, wear resistance, corrosion resistance, high temperature creep resistance, high temperature oxidation resistance, tempering softening resistance and the like, different alloys have different characteristics, the performance of the alloy is obviously superior to that of the traditional alloy, and if the high-entropy alloy powder is prepared by adopting an atomization method, the porous material is prepared by taking the high-entropy alloy powder as a raw material, so that the high-entropy alloy with excellent performance has important significance for the application of the high-entropy alloy in.
However, with the conventional processing method, a billet needs to be manufactured in the processing process, the billet needs to be subjected to high-pressure extrusion forming in the manufacturing process, the billet is prone to having uneven distribution of metal powder particles due to different extrusion directions in the forming process, cracks, uneven porosity and the like are prone to occurring after sintering, and the structural strength of the porous material is seriously affected.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a pre-alloyed 3D formed high-entropy alloy porous material which is convenient for uniform forming of a compact, is convenient for improvement of structural stability and structural strength of the sintered compact, prevents cracks from occurring in the sintering process, is uniform and regular in porosity, and has excellent wear resistance, corrosion resistance and high-temperature oxidation resistance, and a preparation method thereof.
The technical scheme of the invention is as follows: a preparation method of a pre-alloyed 3D formed high-entropy alloy porous material adopts high-entropy alloy powder as a raw material, a three-dimensional grid structure as a frame, and a porous sintered body sintered by the high-entropy alloy powder is nested in the porous material, and the preparation method mainly comprises the following steps:
the first step, powder treatment: accurately weighing and proportioning Cr, Mo, Nb, Ta and V metal powder according to an equimolar proportion, and uniformly mixing the metal powder for later use;
step two, atomizing to prepare powder: putting the mixed powder of Cr, Mo, Nb, Ta and V in the first step into a medium-frequency induction smelting furnace to be molten into metal liquid; introducing high-speed jet argon gas flow through a nozzle to impact and shear the metal flow, so that the metal flow is broken into fine metal liquid drops; then the liquid drop is quenched in pure argon gas to form solid powder particles; the undersize product of the solid powder particles after sieving is the required pre-alloyed powder sample;
thirdly, establishing a three-dimensional solid model of the high-entropy alloy porous sintered body frame in a computer by utilizing three-dimensional modeling software according to the shape and the size of the frame of the porous material to be prepared;
step four, importing the data of the three-dimensional solid model in the step three into layer cutting software, and carrying out layer cutting processing on the three-dimensional solid model to obtain original data of a two-dimensional layer cutting;
fifthly, introducing the original data of the two-dimensional slice layer in the fourth step into a rapid prototyping machine, selecting metal powder with the same material as the high-entropy alloy porous material to be prepared as a raw material, and preparing a frame of the high-entropy alloy porous sintered body by adopting a 3D printing method; the 3D printing powder spreading thickness is 0.02mm-0.04 mm;
and sixthly, reserving CrMoNbTaV high-entropy alloy powder inside a three-dimensional grid structure in the frame according to the design requirement of the high-entropy alloy porous sintered body to be prepared, then placing the frame in a horizontal graphite sintering furnace for vacuum sintering for 1-10h, and cooling along with the furnace after sintering to obtain the CrMoNbTaV high-entropy alloy porous material.
The method has the advantages of effectively solving the problem of uneven distribution of metal particles in the forming process of the compact, effectively improving the sintering effect of the compact, improving the structural stability and structural strength of the porous material, effectively reducing the occurrence of cracks in the sintering process, enabling the porosity to be according to even rules, effectively improving the characteristics of the porous material such as wear resistance, corrosion resistance, high-temperature oxidation resistance and the like, facilitating the promotion of the use value and facilitating the wide application.
Further, the purity of the metallic starting material such as Cr, Mo, Nb, Ta, and V described in the first step is 99.5% or more.
Further, the temperature in the medium-frequency induction smelting furnace in the second step is 1500-2800 ℃; the size of a nozzle gap is 0.5-1.0 mm, and the spray angle is 30-60 degrees; the solid powder particles are sieved by a sieve with 100-500 meshes.
Preferably, the temperature in the medium-frequency induction smelting furnace in the second step is 2500-2800 ℃; the size of a nozzle gap is 0.5-1.0 mm, and the spray angle is 40-60 degrees; the solid powder particles are sieved by a 200-500-mesh sieve.
Preferably, the temperature in the medium-frequency induction smelting furnace in the second step is 2600 ℃; the size of the nozzle gap is 0.8mm, and the spray angle is 50 degrees; the solid powder particles are sieved by a 300-mesh sieve.
Furthermore, the grain diameter of the atomized pre-alloyed powder in the second step is 4-15 μm. The atomization method adopted in the second step is used for producing alloying powder, the prepared high-entropy alloy powder is called pre-alloy powder, each particle prepared by the atomization method not only has uniform chemical components completely the same as those of the established molten alloy, but also has a refined crystalline structure due to the rapid solidification effect, and the macro segregation of a second phase is eliminated.
Preferably, the atomized pre-alloyed powder in the second step has a particle size of 10 μm. The grain diameter of the pre-alloyed powder is not suitable to be too large, the forming effect is poor when the grain diameter is too large, the sedimentation coefficient of a sintered compact is larger, the porosity is too large, the grain diameter is not suitable to be too small, pores with too small grain diameter are easy to fuse, the permeability of the pores is influenced, and the sintering quality and the sintering effect of the porous material are influenced.
Further, the three-dimensional modeling software in the third step may be Pro-E software or UG8.0 software.
Further, the average pore diameter of the micropores in the porous sintered body was 12 μm.
Further, the layer cutting software in the fourth step is SolidWorks software.
Further, the rapid prototyping machine in the fifth step is a 3D printer or a laser rapid prototyping machine, and the process parameters are as follows: the laser scanning speed is 360mm/min-480 mm/min, and the laser power is 1Kw-1.8 Kw.
Further, the vacuum degree of the furnace body in the sixth step is 4.2E-4Pa, and the final sintering temperature of vacuum sintering is 0.6-0.7 times of the melting point of the CrMoNbTaV high-entropy alloy powder; the heat preservation time is 1h-2 h.
The pre-alloyed 3D formed high-entropy alloy porous material is processed and manufactured by the method, and the component of the pre-alloyed 3D formed high-entropy alloy porous material is CrMoNbTaV.
Preferably, the components of the pre-alloyed 3D formed high-entropy alloy porous material are metal raw materials such as Cr, Mo, Nb, Ta and V in equal molar ratio, namely the molar ratio of Cr to Mo to Nb to Ta to V is as follows in sequence: 1:1:1:1:1.
The invention has the following characteristics:
(1) the high-entropy alloy powder produced by the atomization method has uniform chemical components and fine crystals, and provides a high-quality powder raw material for preparing a high-performance porous filtering material by the following powder metallurgy; the prepared porous material has good physical and chemical stability and good corrosion resistance, and provides stable guarantee for subsequent filtration.
(2) High porosity and large specific surface area. The invention utilizes the partial diffusion effect among the element powders in the sintering process to enable the material to generate a large amount of uniformly distributed pores, thereby increasing the specific surface area of the material.
(3) The sintering time is shortened on a large scale.
(4) High corrosion resistance, high oxidation resistance, high chemical stability, high mechanical strength and low corrosion possibility.
(5) The process is simple and environment-friendly, and can be used for batch production. The preparation process is simple and controllable, the raw material utilization rate is high in the production process, no pollution is generated, and industrial production in various countries can be realized.
Detailed Description
The following specific examples are provided to illustrate the manner and process capabilities of the present invention, and other advantages and benefits of the present invention will become apparent to those skilled in the art from the disclosure herein. The invention is further described with reference to specific examples.
A pre-alloyed 3D formed high-entropy alloy porous material is prepared by processing metal raw materials such as Cr, Mo, Nb, Ta and V in equal molar ratio, wherein the molar ratio of Cr to Mo to Nb to Ta to V is as follows in sequence: 1:1:1:1:1, atomizing a metal raw material to prepare powder, and taking CrMoNbTaV high-entropy prealloying powder as a raw material to prepare the porous material.
The preparation method of the pre-alloyed 3D-shaped high-entropy alloy porous material comprises the following specific steps of, using high-entropy alloy powder as a raw material, using a three-dimensional grid structure as a frame, and embedding a porous sintered body sintered by the high-entropy alloy powder in the porous material, wherein the preparation method mainly comprises the following treatment processes:
1. CrMoNbTaV high-entropy porous alloy component design
The porous material to be prepared in this embodiment is a crmonibtav high-entropy porous alloy, and the crmonibtav high-entropy porous alloy is composed of five element metal powders of Cr, Mo, Nb, Ta, and V, wherein the purity of the Cr, Mo, Nb, Ta, and V metal raw materials is more than 99.5%, and the molar ratio of Cr, Mo, Nb, Ta, and V is, in order: 1:1:1:1:1, accurately weighing and proportioning according to the equal molar ratio, and uniformly mixing for later use.
2. Preparation of CrMoNbTaV prealloyed powder
① melting Cr, Mo, Nb, Ta and V powder in a medium frequency induction melting furnace to obtain molten metal (the temperature in the furnace is 2600-2800 ℃), ② introducing high-speed jet argon flow to impact and shear the molten metal to break the molten metal into fine metal droplets, wherein the size of a nozzle gap is 0.5-1.0 mm, the jet angle is 30-60 degrees, ③ rapidly cooling the droplets in 1.8-2.0 MPa pure argon to obtain solid powder particles, and the screen underflow of the ④ solid powder particles after being sieved by a 200-mesh sieve is the required pre-alloyed powder, and the particle size of the pre-alloyed powder is 4-15 mu m.
3. Forming and preparing CrMoNbTaV pre-alloyed high-entropy porous body
According to the shape and the size of a frame to be prepared, a three-dimensional solid model of the frame of the high-entropy porous alloy sintered body is established in a computer by utilizing three-dimensional modeling software UG8.0 or Pro-E software, the size of a three-dimensional grid structure grid is (mm) multiplied by (mm), and the average pore diameter of micropores in the porous sintered body is 12 mu m; importing the data of the three-dimensional solid model into layer cutting software SolidWorks, and carrying out layer cutting processing on the three-dimensional solid model to obtain the original data of a two-dimensional slice layer; and then, introducing the original data of the two-dimensional sliced layer into a rapid prototyping machine, wherein the rapid prototyping machine is a 3D printer or a laser rapid prototyping machine, the obtained pre-alloyed powder is used as a raw material, a frame of the high-entropy alloy porous sintered body is prepared by the laser rapid prototyping machine by a 3D printing method, and the 3D printing process parameters are as follows: the laser scanning speed is 360-480 mm/min, the laser power is 1-1.8 Kw, and the 3D printing powder laying thickness parameter is 0.02-0.04 mm; then placing the frame in a horizontal graphite sintering furnace for vacuum sintering, wherein the vacuum degree of the furnace body is 4.2E-4Pa, and cooling along with the furnace to obtain a high-entropy alloy porous material; the final sintering temperature of the vacuum sintering is 0.6-0.7 times of the melting point of the high-entropy alloy powder, and the heat preservation time is 1-2 h.
4. CrMoNbTaV prealloyed high-entropy porous body structure and performance
1) X-ray diffraction (XRD) test and phase composition analysis of high-entropy porous material
The obtained ingot was cut into square samples of 4mm × 4mm × 3 mm size by wire cutting, and the samples were finely ground with metallographic abrasive paper of 800 #, 1200 #, 1500 # and 2000 # in this order, and polished with a polisher. X-ray diffraction phase analysis was performed on a Rigaku D/Max 2500X-ray diffractometer, Japan. The technical specification of the equipment is as follows: cu was used as a radiation source, a graphite monochromator, an operating voltage of 40 kV, a current of 250 mA, and a spinning target. The scan rate is 8 °/min, and the diffraction angle range is chosen to be 2 θ =5-90 °. The experimental data are analyzed by using MDI-Jade 6.0 software, and the XRD test result of the CrMoNbTaV high-entropy alloy shows that the main composition phase of the CrMoNbTaV high-entropy porous alloy is a body-centered cubic structure and a small amount of Laves phase. The Laves phase is mainly Cr2Nb、V2A Ta intermetallic compound.
2) High-entropy porous alloy material microstructure analysis
The obtained ingot was cut into square samples of 4mm × 4mm × 3 mm size by wire cutting, and the samples were finely ground with metallographic abrasive paper of 800 #, 1200 #, 1500 # and 2000 # in this order, and polished with a polisher. And observing the tissue morphology of the sample by using a scanning electron microscope. The crystal grains generated by the CrMoNbTaV high-entropy alloy are in a dendritic form and are uniformly distributed, so that the structural stability and structural strength of the porous material are effectively improved, and the economic value of the porous material is conveniently improved.
3) Corrosion resistance of high-entropy porous alloy material
The obtained ingot was cut into square samples of 4mm × 4mm × 3 mm size by wire cutting, and the samples were finely ground with metallographic abrasive paper of 800 #, 1200 #, 1500 # and 2000 # in this order, and polished with a polisher. Putting the grinded and polished sample into alcohol, cleaning for 30 min by using an ultrasonic cleaner, drying and weighing, and then completely soaking the sample into HNO with the concentration of 5%, 15% and 30% respectively3The solution and 3.5% NaCl solution were kept for 6 hours, 12 hours, 24 hours, 48 hours, and 96 hours, and then taken out, and the surface state and weight change of the sample before and after the corrosion were analyzed.
The mass change of the CrMoNbTaV high-entropy alloy porous material after being soaked in 3.5% NaCl solution and 5%, 15% and 30% HNO3 solution for 96 hours in the example is shown in the following table 1.
TABLE 1 test result of 96h etching test of CrMoNbTaV high-entropy alloy porous material
| Etching solution | 3.5%NaCl | 5% HNO3 | 15% HNO3 | 30% HNO3 |
| Mass/g before etching | 0 .4084 | 0 .3974 | 0 .4177 | 0 .3560 |
| Mass/g after etching | 0 .4085 | 0 .3980 | 0 .4180 | 0 .3567 |
| Change in mass/g | 0 .0001 | 0 .0006 | 0 .0003 | 0 .0007 |
As seen from the table 1, the mass change of the porous alloy in different corrosive liquids is small, and the surface of the alloy is almost unchanged, which shows that the CrMoNbTaV high-entropy alloy porous material prepared by the method has excellent corrosion resistance.
The scheme effectively solves the problem of uneven distribution of metal particles in the forming process of the compact, effectively improves the sintering effect of the compact and the structural stability and structural strength of the porous material, reduces the occurrence of cracks in the sintering process, enables the porosity to be uniform and regular, effectively improves the characteristics of wear resistance, corrosion resistance, high-temperature oxidation resistance and the like of the porous material, facilitates the promotion of the use value of the porous material, and is convenient for wide application.
The preferred embodiments of the invention have been described in detail above, but it is apparent that the invention is not limited to the above embodiments only. Within the scope of the inventive idea, many equivalent variations can be made to the inventive solution, all falling within the scope of protection of the invention. In addition, it should be noted that the respective technical features described in the above-described embodiments may be separately and independently combined as long as they are within the technical concept of the invention.
Claims (10)
1. A preparation method of a pre-alloyed 3D formed high-entropy alloy porous material is characterized in that the porous material adopts high-entropy alloy powder as a raw material, a three-dimensional grid structure is used as a frame, and a porous sintered body sintered by the high-entropy alloy powder is nested in the porous material, and the preparation method mainly comprises the following steps:
the first step, powder treatment: accurately weighing and proportioning Cr, Mo, Nb, Ta and V metal powder according to an equimolar proportion, and uniformly mixing the metal powder for later use;
step two, atomizing to prepare powder: putting the mixed powder of Cr, Mo, Nb, Ta and V in the first step into a medium-frequency induction smelting furnace to be molten into metal liquid; introducing high-speed jet argon gas flow through a nozzle to impact and shear the metal flow, so that the metal flow is broken into fine metal liquid drops; then the liquid drop is quenched in pure argon gas to form solid powder particles; the undersize product of the solid powder particles after sieving is the required pre-alloyed powder sample;
thirdly, establishing a three-dimensional solid model of the high-entropy alloy porous sintered body frame in a computer by utilizing three-dimensional modeling software according to the shape and the size of the frame of the porous material to be prepared;
step four, importing the data of the three-dimensional solid model in the step three into layer cutting software, and carrying out layer cutting processing on the three-dimensional solid model to obtain original data of a two-dimensional layer cutting;
fifthly, introducing the original data of the two-dimensional slice layer in the fourth step into a rapid prototyping machine, selecting metal powder with the same material as the high-entropy alloy porous material to be prepared as a raw material, and preparing a frame of the high-entropy alloy porous sintered body by adopting a 3D printing method; the 3D printing powder spreading thickness is 0.02mm-0.04 mm;
and sixthly, reserving CrMoNbTaV high-entropy alloy powder inside a three-dimensional grid structure in the frame according to the design requirement of the high-entropy alloy porous sintered body to be prepared, then placing the frame in a horizontal graphite sintering furnace for vacuum sintering for 1-10h, and cooling along with the furnace after sintering to obtain the CrMoNbTaV high-entropy alloy porous material.
2. The preparation method of the pre-alloyed 3D-shaped high-entropy alloy porous material according to claim 1, characterized in that: the purity of the metal raw materials such as Cr, Mo, Nb, Ta and V in the first step is more than 99.5%.
3. The preparation method of the pre-alloyed 3D-shaped high-entropy alloy porous material according to claim 1, characterized in that: the temperature in the medium-frequency induction smelting furnace in the second step is 1500-2800 ℃; the size of a nozzle gap is 0.5-1.0 mm, and the spray angle is 30-60 degrees; the solid powder particles are sieved by a sieve with 100-500 meshes.
4. The preparation method of the pre-alloyed 3D-shaped high-entropy alloy porous material according to claim 1, characterized in that: the grain diameter of the atomized prealloy powder in the second step is 4-15 μm.
5. The preparation method of the pre-alloyed 3D-shaped high-entropy alloy porous material according to claim 1, characterized in that: the three-dimensional modeling software in the third step may be Pro-E software or UG8.0 software.
6. The preparation method of the pre-alloyed 3D-shaped high-entropy alloy porous material according to claim 1, characterized in that: the average pore diameter of micropores in the porous sintered body was 12 μm.
7. The preparation method of the pre-alloyed 3D-shaped high-entropy alloy porous material according to claim 1, characterized in that: and the layer cutting software in the fourth step is SolidWorks software.
8. The preparation method of the pre-alloyed 3D-shaped high-entropy alloy porous material according to claim 1, characterized in that: the rapid forming machine in the fifth step is a 3D printer or a laser rapid forming machine, and the process parameters are as follows: the laser scanning speed is 360mm/min-480 mm/min, and the laser power is 1Kw-1.8 Kw.
9. A method of preparing a pre-alloyed 3D shaped high entropy alloy porous material according to any one of claims 1 to 8, characterized in that: in the sixth step, the vacuum degree of the furnace body is 4.2E-4Pa, and the final sintering temperature of vacuum sintering is 0.6-0.7 times of the melting point of the CrMoNbTaV high-entropy alloy powder; the heat preservation time is 1h-2 h.
10. A prealloyed 3D formed high-entropy alloy porous material is characterized in that: the pre-alloyed 3D formed high-entropy alloy porous material is processed and manufactured by the method according to any one of claims 1 to 9, and the component of the pre-alloyed 3D formed high-entropy alloy porous material is CrMoNbTaV.
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