CN109570513B - Preparation method of porous metal powder - Google Patents
Preparation method of porous metal powder Download PDFInfo
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- CN109570513B CN109570513B CN201910034414.9A CN201910034414A CN109570513B CN 109570513 B CN109570513 B CN 109570513B CN 201910034414 A CN201910034414 A CN 201910034414A CN 109570513 B CN109570513 B CN 109570513B
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- 239000004917 carbon fiber Substances 0.000 claims abstract description 111
- 238000000498 ball milling Methods 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 40
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- 238000000137 annealing Methods 0.000 abstract description 35
- 239000002245 particle Substances 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 16
- 239000011148 porous material Substances 0.000 abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 238000003860 storage Methods 0.000 abstract description 10
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- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
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- 230000001681 protective effect Effects 0.000 abstract description 3
- 239000012188 paraffin wax Substances 0.000 abstract description 2
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- 239000002994 raw material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 238000004321 preservation Methods 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
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- 238000004513 sizing Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 229910000568 zirconium hydride Inorganic materials 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- B22F1/0007—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The invention relates to a preparation method of porous metal powder, belonging to the technical field of metal powder. The preparation method comprises the following steps: the method comprises the steps of degumming short carbon fibers, carrying out a proper ball milling process on the degummed short carbon fibers and metal powder to obtain metal powder embedded with ultrafine carbon particles, carrying out annealing treatment in oxygen-containing air to remove the carbon particles, and finally annealing in reducing atmosphere or protective atmosphere or vacuum to obtain the high-purity porous metal powder with uniform and highly dispersed pores. In the porous metal powder prepared by the invention, the size of metal particles is adjustable, the porosity is controllable, and the pore size is 1-3 mu m. The prepared material has good oil storage, hydrogen storage, paraffin storage and lithium storage performances, and is simple in preparation process and low in cost.
Description
Technical Field
The invention relates to a preparation method of porous metal powder, belonging to the technical field of metal powder.
Background
The porous metal material is a novel metal material containing a large number of connected or closed pores in a matrix. Compared with dense metal, the porous metal has good compressibility, and the Poisson ratio can be changed in the deformation process; compared with polymer foam, the polyurethane foam has high rigidity and high use temperature, and can not be dissolved by organic solvent; compared with foamed ceramic, it has excellent toughness, heat conducting performance and electric conductivity. Because of its excellent performance, it has a wide prospect in the fields of automobile industry, aerospace, environmental protection, building and the like.
The preparation process of the porous metal material mainly comprises three major methods, namely a liquid metal solidification method, a solid metal sintering method and a metal deposition method. Wherein the melt-foaming process is by means of metal hydrides, e.g. TiH2Or ZrH2Etc. are added to the molten metal as a blowing agent, and the gas is released by heating to decompose the blowing agent, and cooling the molten liquid stream can cause the gas to be sealed inside the metal to form a porous metal. The method is generally suitable for metal materials with low melting points, such as aluminum, magnesium and the like, has simple process, lower cost and high porosity of the prepared sample,but bubble size and pore uniformity are difficult to control. The preparation method for preparing the porous metal powder with controllable metal particle size, porosity and pore size is the current technical problem.
Chinese patent CN 108232160 a discloses a method for preparing a porous metal-carbon composite material with high metal content and high dispersity. The compound MX of the target metal and the carbide of the active metal A are subjected to mechanical ball milling reaction, and the carbide of the A is a reducing agent and a carbon source. Thus, carbon is generated in situ when MX is reduced to a metal, thereby achieving highly dispersed complexing of the metal particles with the carbon material, and the content of the metal is determined by the stoichiometric ratio of the chemical reaction. In the porous composite material prepared by the invention, the size of the metal particles is adjustable, and the porosity is controllable. The prepared material shows good sodium and lithium storage performance.
The Chinese invention patent CN 102274975A discloses a method for preparing metal micro-nano hollow sphere powder, which mainly comprises the following steps: the tool electrode and the workpiece electrode correspondingly immerse in the working solution with a gap required by spark discharge, a pulse power supply is switched on to enable the tool electrode and the workpiece electrode to be subjected to spark discharge melting and gasification, meanwhile, ultrasonic frequency vibration is carried out on the working solution between the tool electrode and the workpiece electrode in the spark discharge process, the working solution in the gap generates micro bubbles, and metal materials which are melted and gasified by the tool electrode and the workpiece electrode are attached and deposited on the surfaces of the micro bubbles to form the metal micro-nano hollow sphere. The metal micro-nano hollow sphere powder prepared by the method has high hollow degree of the hollow sphere, the particle size distribution of the hollow sphere is between 20nm and 100 mu m, the wall thickness is not more than 1 mu m, and the hollow sphere proportion is high. The preparation method has the defects of complex process, low production efficiency, high production cost, difficult clean removal of the template and easy environmental pollution.
The invention Chinese patent CN 105506336A discloses a method for preparing porous metal by high-temperature oxidation and reduction, the invention relates to a method for preparing porous metal, namely, firstly, cleaning metal material; secondly, heating the supporting body to 100-850 ℃ under the protection of inert gas, and then exposing the metal material in oxidizing gas for oxidation treatment; and thirdly, exhausting oxidizing gas, heating to 300-850 ℃, exposing the metal oxide in reducing gas for reduction treatment, and cooling under the protection of inert gas to obtain the porous metal. The invention directly utilizes the oxidizing and reducing gases to form a micron-scale porous structure on the surface and inside of the metal, has simple preparation process and can realize secondary processing on the prepared complex metal material device. However, the pore size obtained by the method is too small (micron-sized), spontaneous diffusion and enrichment of oxygen on the surface and in the material are required to occur, a porous metal structure is finally formed, the diffusion and enrichment of oxygen are difficult to control, and the size and uniformity of the porosity of the metal are difficult to control.
So far, no description is found about the preparation of porous metal powder by high-energy ball milling combined with oxidation-reduction treatment.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a method for preparing porous metal powder, which is simple and low-cost, and solves the problems of controllable size of metal particles, porosity and pore size, and the prepared material shows good oil storage, hydrogen storage, paraffin storage and lithium storage properties, and has a simple preparation process and low cost.
The invention relates to a preparation method of porous metal powder, which comprises the steps of carrying out high-energy ball milling on degummed short carbon fiber and metal powder, firstly carrying out first heat treatment in an oxidizing atmosphere, and then carrying out second heat treatment in a non-oxidizing atmosphere to obtain the porous metal powder.
The preparation process of the degummed short carbon fiber comprises the following steps: and (3) carrying out heat treatment on the short carbon fiber bundle at 650-800 ℃ for 20-90 min under a protective atmosphere to obtain the carbon fiber bundle. The surface of the carbon fiber is coated with the solidified organic colloid layer, the sizing agent on the surface of the carbon fiber is removed after degumming treatment, and the roughness of the surface of the carbon fiber is increased, so that the subsequent ball milling treatment can remove the constraint/limitation of the sizing agent, remove impurities and active functional groups on the surface of the carbon fiber, and improve the breaking rate of the short carbon fiber.
The protective atmosphere is an inert atmosphere or vacuum, such as nitrogen, argon.
The diameter of the short carbon fiber bundle is 6-8 mu m, and the length of the short carbon fiber bundle is 1-4 mm.
The short fiber is too long, and is easy to wind and agglomerate during ball milling, and the too short fiber not only increases the cost, but also has larger separation difficulty.
Preferably, the volume ratio of the degummed short carbon fiber to the metal powder is 1-9: 19-1, more preferably 1-4: 9 to 1, and more preferably 1 to 4: 4 to 1.
In the metal powder, the metal element is zero-valent, and the metal element is selected from at least one of Cu, Ti, Fe, Co, Ni, Mo and Ag.
Preferably, the high-energy ball milling mode is planetary ball milling or vibration ball milling.
Preferably, the mass ratio of the total mass of the degummed short carbon fibers and the metal powder in the high-energy ball milling to the grinding balls is 1: 5-8.
The high-energy ball milling speed is 220-350 r/min, and the time is at least 6 h.
The conditions of the first heat treatment are as follows: the temperature is 250-400 ℃. The time is determined by the degree of carbon treatment (which is aimed at forcing the carbon embedded and/or penetrating the metal powder to be completely oxidized). Generally 10-60 min. The time is not too long, which can completely oxidize the metal powder and is easy to crack once completely oxidized; during transfer and storage, cracking in the direction of the pores can result.
The non-oxidizing atmosphere is a reducing atmosphere, an inert atmosphere or vacuum.
The conditions of the second heat treatment are as follows: the temperature is 0.3 to 0.65 times of the melting point of the metal. The time is adjusted according to the requirements of products, and is generally 10-60 min. The purpose of the second heat treatment is to achieve reduction of the partially oxidized metal powder.
According to the preparation method of the porous metal powder, the size, the porosity and the pore size of metal particles are adjusted by adjusting the addition amount of the carbon fibers and the ball milling rotating speed, and the porosity can reach 90%.
The invention relates to a preparation method of porous metal powder; the short carbon fiber is degummed. The surface of the existing carbon fiber on the market is coated and solidified with an organic colloid layer, and the surface sizing agent of the carbon fiber is removed through degumming treatment, so that the roughness of the surface of the carbon fiber is increased, the subsequent (grinding) treatment can remove the 'constraint/limitation' of the sizing agent, the impurities on the surface of the carbon fiber are removed, and otherwise, the breakage rate is very low. The invention strictly controls the length of the short carbon fiber as the raw material and needs to be a product after degumming treatment, and aims to well realize the superfine of the carbon fiber, the uniform embedding of the carbon fiber in metal particles and the control of the size of the metal particles by matching the ball milling rotating speed, the grinding balls and the proportion, and obtain the porous metal powder by combining the decarbonization and the deoxidation annealing treatment after ball milling.
The pore diameter of the porous metal powder designed and prepared by the invention is only 1-3 mu m corresponding to the size of the superfine carbon particles, and the porous metal powder is uniformly distributed.
The invention firstly tries to prepare the porous metal powder by adopting the short carbon fiber prepared by the degumming treatment process through the processes of high-energy ball milling with proper ball milling parameters, decarbonization and deoxidation annealing.
Principle and advantages:
(1) short carbon fibers are selected. Because a large number of active functional groups exist on the surface of the carbon fiber, the long carbon fiber is directly used for crushing, the fibers are easy to agglomerate and cannot be crushed, and therefore, the problem can be avoided by selecting the short carbon fiber.
(2) Short carbon fiber treatment method. The degumming process is firstly adopted, because the surface of the commercial carbon fiber is coated with the solidified colloid layer, the carbon fiber surface sizing agent must be removed through the degumming process, so that the subsequent (grinding) treatment can remove the 'constraint/restriction' of the sizing agent, impurities and active functional groups on the surface of the carbon fiber are removed through the degumming process, and otherwise, the breakage rate is low. And then, the ball milling process, the ball milling rotating speed, the grinding balls and the proportion are optimized, so that the superfine carbon fiber can be well realized. And finally, a decarbonizing and deoxidizing annealing process is carried out to remove carbon fiber particles and reduce the oxidized metal powder to obtain the porous metal powder with high purity.
The shape of the porous metal powder prepared by combining the short carbon fiber degummed at 700 ℃ at 250r/min and the metal powder high-energy ball milling method with the air annealing at 300 ℃ and the hydrogen annealing at 350 ℃ is shown in figure 2.
As can be seen from fig. 2, the degumming treatment combined with the suitable high-energy ball milling process and the subsequent decarbonization-deoxidation and impurity removal annealing process can obtain the porous metal powder with controllable pore diameter and porosity and uniform pores.
In a word, the method has the advantages of simple preparation process (only degumming, ball milling, decarbonization, deoxidation, impurity removal and annealing), low cost, excellent and uniform performance of the obtained porous metal powder and good market prospect.
Drawings
FIG. 1 is a flow chart of the preparation of porous metal powder according to the present invention;
FIG. 2 is a powder SEM appearance prepared by a high-energy ball milling method of 700 ℃ degummed short carbon fiber and metal powder at 250r/min and combining air annealing at 300 ℃ and hydrogen annealing at 350 ℃.
Fig. 1 shows a process for preparing the porous metal powder according to the present invention, which specifically comprises: the method comprises the steps of degumming short carbon fibers, carrying out a proper ball milling process on the degummed short carbon fibers and metal powder to obtain metal powder embedded with ultrafine carbon particles, carrying out annealing treatment in oxygen-containing air to remove the carbon particles, and finally carrying out hydrogen reduction to obtain porous metal powder with uniform and highly dispersed pores.
As shown in FIG. 2, the degumming treatment is combined with a suitable high-energy ball milling process and a decarbonization-deoxidation impurity removal annealing process to obtain the porous metal powder with the aperture of about 1-3 μm and uniformly distributed pores.
Detailed Description
The technical solutions of the present invention are clearly and completely described below with reference to the drawings of the present invention, and it is obvious that the described embodiments are only some of the technical solutions described in the present invention, but not all of the technical solutions described in the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Comparative example 1
In the comparative example 1, scaly graphite with the particle size of 120 microns and electrolytic copper powder with the particle size of 120 microns are used as ball milling raw materials, the volume percentage of the natural scaly graphite is 20%, the volume percentage of the electrolytic copper powder is 80%, the scaly graphite and the electrolytic copper powder are added into ball milling equipment for high-energy ball milling, the rotating speed is 250r/min, the ball milling time is 6 hours, and the ball-to-material ratio is 5: 1. The natural flake graphite spontaneously agglomerated and did not break. After exactly the same subsequent treatment as in example 1, no porous metal powder was obtained.
Comparative example 2
The comparative example 2 adopts the granular graphite with the grain diameter of 120 mu m and the electrolytic copper powder with the grain diameter of 120 mu m as ball milling raw materials, the volume percentage of the granular graphite is 20 percent, the electrolytic copper powder is added into the ball milling equipment for high-energy ball milling, the rotating speed is 250r/min, the ball milling time is 6h, and the ball-to-material ratio is 5: 1. The particulate graphite fraction was broken up and not significantly embedded in the copper powder. After exactly the same subsequent treatment as in example 1, no porous metal powder was obtained.
Comparative example 3
In the comparative example 3, commercially available short carbon fibers without any pretreatment and electrolytic copper powder with the particle size of 120 mu m are used as ball milling raw materials, the volume percentage of the carbon fibers is 20 percent, the volume percentage of the electrolytic copper powder is 80 percent, the diameter of the short carbon fibers is 8 mu m, the length of the short carbon fibers is 2mm, the short carbon fibers and the electrolytic copper powder are added into ball milling equipment for high-energy ball milling, the rotating speed is 250r/min, the ball milling time is 6h, and the ball-to-material ratio is 5: 1. The short carbon fibers are not broken and are adhered to the wall of the ball milling pot. After exactly the same subsequent treatment as in example 1, no porous metal powder was obtained.
Comparative example 4
In the comparative example 4, commercially available short carbon fibers subjected to degumming treatment at 1000 ℃ and electrolytic copper powder with the particle size of 120 mu m are used as ball milling raw materials, the volume percentage of the short carbon fibers is 20%, the volume percentage of the electrolytic nickel powder is 80%, the diameter of the short carbon fibers is 8 mu m, the length of the short carbon fibers is 2mm, the short carbon fibers and the electrolytic copper powder are added into ball milling equipment for high-energy ball milling, the rotating speed is 250r/min, the ball milling time is 6h, and the ball-to-material ratio is 5: 1. The short carbon fibers did not break down significantly. After exactly the same subsequent treatment as in example 1, no porous metal powder was obtained.
Comparative example 5
In the comparative example 5, commercially available short carbon fibers subjected to degumming treatment at 700 ℃ and electrolytic copper powder with the particle size of 120 mu m are used as ball milling raw materials, the volume percentage of the short carbon fibers is 20%, the volume percentage of the electrolytic nickel powder is 80%, the diameter of the short carbon fibers is 12 mu m, the length of the short carbon fibers is 2mm, the short carbon fibers and the electrolytic copper powder are added into ball milling equipment for high-energy ball milling, the rotating speed is 250r/min, the ball milling time is 6h, and the ball-to-material ratio is 5: 1. The short carbon fibers did not break down significantly and after the same post-treatment as in example 1, no porous metal powder was obtained.
Comparative example 6
In the comparative example 6, commercially available short carbon fibers subjected to degumming treatment at 700 ℃ and electrolytic nickel powder with the particle size of 120 microns are used as ball milling raw materials, the volume percentage of the short carbon fibers is 20%, the volume percentage of the electrolytic nickel powder is 80%, the diameter of the short carbon fibers is 6 microns, the length of the short carbon fibers is 2mm, the short carbon fibers and the electrolytic nickel powder are added into ball milling equipment for high-energy ball milling, the rotating speed is 600r/min, the ball milling time is 6 hours, and the ball-to-material ratio is 6: 1. The short carbon fibers did not break down significantly and were mostly deposited on the top lid of the ball mill jar.
Comparative example 7
In the comparative example 7, commercially available short carbon fibers subjected to degumming treatment at 700 ℃ and electrolytic nickel powder with the particle size of 120 microns are used as ball milling raw materials, the volume percentage of the short carbon fibers is 20%, the volume percentage of the electrolytic nickel powder is 80%, the diameter of the short carbon fibers is 6 microns, the length of the short carbon fibers is 2mm, the short carbon fibers and the electrolytic nickel powder are added into ball milling equipment for high-energy ball milling, the rotating speed is 100r/min, the ball milling time is 6 hours, and the ball-to-material ratio is 6: 1. The short carbon fibers did not break down significantly and after the same post-treatment as in example 1, no porous metal powder was obtained.
Example 1
In the embodiment 1, commercially available short carbon fibers degummed at 700 ℃ for 60min and electrolytic copper powder with the particle size of 120 microns are used as ball milling raw materials, the volume percentage of the short carbon fibers is 10%, the volume percentage of the electrolytic copper powder is 90%, the diameter of the short carbon fibers is 6 microns, the length of the short carbon fibers is 2mm, the short carbon fibers and the electrolytic copper powder are added into ball milling equipment for high-energy ball milling, the rotating speed is 250r/min, the ball milling time is 6 hours, the ball-to-material ratio is 6:1, then annealing and decarbonization are carried out in air, the annealing temperature is 300 ℃, the heat preservation time is 20min, then deoxidation is carried out in a hydrogen atmosphere, the annealing temperature is 350 ℃, the heat preservation time is 30min, and the porosity of the obtained porous copper powder reaches 9%.
Example 2
In this example 2, commercially available short carbon fibers degummed at 750 ℃ for 60min and electrolytic nickel powder with a particle size of 120 μm are used as ball milling raw materials, the volume percentage of the short carbon fibers is 25%, the electrolytic nickel powder is added into the ball milling raw materials, the volume percentage of the short carbon fibers is 75%, the diameter of the short carbon fibers is 6 μm, the length of the short carbon fibers is 2mm, the short carbon fibers and the electrolytic nickel powder are added into ball milling equipment for high-energy ball milling, the rotating speed is 280r/min, the ball milling time is 7h, the ball-to-material ratio is 6:1, then annealing and decarbonization are performed in air, the annealing temperature is 300 ℃, the heat preservation time is 30min, annealing is performed in a hydrogen atmosphere, the annealing temperature is 500 ℃, the heat preservation time is 20min, and the porosity of the obtained porous nickel powder reaches 22%.
Example 3
In this example 3, commercially available short carbon fibers degummed at 800 ℃ for 60min and reduced iron powder with a particle size of 150 μm are used as ball milling raw materials, the volume percentage of the short carbon fibers is 40%, the reduced iron powder is added into the ball milling equipment, the volume percentage of the short carbon fibers is 60%, the diameter of the short carbon fibers is 6 μm, the length of the short carbon fibers is 2mm, the short carbon fibers and the reduced iron powder are added into the ball milling equipment for high-energy ball milling, the rotating speed is 300r/min, the ball milling time is 8h, the ball-to-material ratio is 6:1, then annealing and decarbonization are performed in the air, the annealing temperature is 300 ℃, the heat preservation time is 20min, then deoxidation is performed in a hydrogen atmosphere, the annealing temperature is 500 ℃, the heat preservation time is 30min, and the porosity of the obtained porous iron powder reaches 38%.
Example 4
In this embodiment 4, commercially available short carbon fibers degummed at 750 ℃ for 60min and spherical titanium powder with a particle size of 50 μm are used as ball milling raw materials, the volume percentage of the short carbon fibers is 55%, the volume percentage of the spherical titanium powder is 45%, the diameter of the short carbon fibers is 7 μm, the length of the short carbon fibers is 2mm, the short carbon fibers and the spherical titanium powder are added into ball milling equipment for high-energy ball milling, the rotating speed is 250r/min, the ball milling time is 10h, the ball-to-material ratio is 7:1, then annealing and decarbonization are performed in air, the annealing temperature is 300 ℃, the heat preservation time is 20min, deoxidation is performed in a hydrogen atmosphere, the annealing temperature is 600 ℃, the heat preservation time is 30min, and the porosity of the obtained porous titanium powder reaches 50%.
Example 5
In this embodiment 5, commercially available short carbon fibers degummed at 800 ℃ for 60min and spherical silver powder with a particle size of 180 μm are used as ball milling raw materials, the volume percentage of the short carbon fibers is 65%, the spherical silver powder is added to 35%, the diameter of the short carbon fibers is 8 μm, the length of the short carbon fibers is 2mm, the short carbon fibers and the spherical silver powder are added to ball milling equipment for high-energy ball milling, the rotating speed is 280r/min, the ball milling time is 8h, the ball-to-material ratio is 6:1, then annealing and decarbonization are performed in air, the annealing temperature is 280 ℃, the heat preservation time is 20min, then deoxidation is performed in vacuum, the annealing temperature is 300 ℃, the heat preservation time is 10min, and the porosity of the obtained porous silver powder reaches 60%.
Example 6
In this example 6, commercially available short carbon fibers degummed at 750 ℃ for 60min and spherical cobalt powder with a particle size of 150 μm are used as ball milling raw materials, the volume percentage of the short carbon fibers is 80%, the volume percentage of the spherical cobalt powder is 20%, the diameter of the short carbon fibers is 8 μm, the length of the short carbon fibers is 2mm, the short carbon fibers and the spherical cobalt powder are added into ball milling equipment for high-energy ball milling, the rotating speed is 280r/min, the ball milling time is 8h, the ball-to-material ratio is 6:1, then annealing and decarbonization are performed in air, the annealing temperature is 300 ℃, the heat preservation time is 20min, then deoxidation is performed in a hydrogen atmosphere, the annealing temperature is 500 ℃, the heat preservation time is 20min, and the porosity of the obtained porous cobalt powder reaches 75%.
Example 7
In this example 7, commercially available short carbon fibers degummed at 750 ℃ for 60min and molybdenum powder with a particle size of 200 μm are used as ball milling raw materials, the volume percentage of the short carbon fibers is 90%, the molybdenum powder is added by 10%, the diameter of the short carbon fibers is 8 μm, the length of the short carbon fibers is 2mm, the short carbon fibers and the molybdenum powder are added into ball milling equipment for high-energy ball milling, the rotation speed is 280r/min, the ball milling time is 10h, the ball-to-material ratio is 6:1, then annealing and decarbonization are performed in the air, the annealing temperature is 320 ℃, the heat preservation time is 20min, then deoxidation is performed in a hydrogen atmosphere, the annealing temperature is 950 ℃, the heat preservation time is 60min, and the porosity of the obtained porous molybdenum powder.
Claims (5)
1. A method of preparing a porous metal powder, comprising: firstly, carrying out high-energy ball milling on degummed short carbon fibers and metal powder with the diameter of 6-8 mu m and the length of 1-4 mm according to the volume ratio of 1-9: 19-1, wherein the high-energy ball milling rotating speed is 220-350 r/min, the time is at least 6h, and the mass ratio of the total mass of the degummed short carbon fibers and the metal powder to the mass of a grinding ball is 1: 5-8;
then carrying out a first heat treatment under an oxidizing atmosphere, the conditions of the first heat treatment being: the temperature is 250-400 ℃, and the time is 10-60 min;
finally, carrying out a second heat treatment under a non-oxidizing atmosphere, wherein the conditions of the second heat treatment are as follows: the temperature is 0.3-0.65 times of the melting point of the metal, and the time is 10-60 min;
thus obtaining the porous metal powder.
2. The production method according to claim 1, characterized in that; the preparation process of the degummed short carbon fiber comprises the following steps: and (3) carrying out heat treatment on the short carbon fiber bundle at 650-800 ℃ for 20-90 min under an inert atmosphere or vacuum condition to obtain the carbon fiber bundle.
3. The method of claim 1, wherein: in the metal powder, the metal element is zero-valent, and the metal element is selected from at least one of Cu, Ti, Fe, Co, Ni, Mo and Ag.
4. The method of claim 1, wherein: the high-energy ball milling mode is planetary ball milling or vibration ball milling.
5. The method of claim 1, wherein:
the non-oxidizing atmosphere is a reducing atmosphere, an inert atmosphere or vacuum.
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