CN109702211B - Preparation method and application of superfine carbon powder - Google Patents
Preparation method and application of superfine carbon powder Download PDFInfo
- Publication number
- CN109702211B CN109702211B CN201910034512.2A CN201910034512A CN109702211B CN 109702211 B CN109702211 B CN 109702211B CN 201910034512 A CN201910034512 A CN 201910034512A CN 109702211 B CN109702211 B CN 109702211B
- Authority
- CN
- China
- Prior art keywords
- powder
- carbon powder
- superfine
- carbon
- soft
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- B22F1/12—Metallic powder containing non-metallic particles
-
- 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
- B22F1/16—Metallic particles coated with a non-metal
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/02—Pretreatment of the fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Powder Metallurgy (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to superfine carbon powder and a preparation method and application thereof, belonging to the technical field of powder. The superfine carbon powder with a special structure is obtained by degumming short carbon fiber and then ball-milling and separating with the assistance of soft metal powder. The superfine carbon powder obtained by the method has uniform granularity, narrow granularity distribution and good dispersibility; meanwhile, the superfine carbon powder also keeps the microscopic crystal structure of the carbon fiber, so that the carbon fiber has the strength and high conductivity. Excellent oxidation resistance and the like. The invention successfully solves the problems of long technological process, complex technological period, large equipment investment and obvious damage to the integrity of graphite or fiber crystal structure in the carbon ultrafine grinding technology, and the designed and prepared ultrafine carbon powder has excellent performance, simple preparation technology and low cost.
Description
Technical Field
The invention relates to superfine carbon powder, in particular to superfine carbon powder and a preparation method and application thereof, belonging to the field of carbon material preparation.
Background
The superfine carbon powder (including graphite powder, carbon fiber powder and the like) has the granularity of less than 10 mu m, has the characteristics of low melting point, high chemical activity, strong magnetism, good heat conduction, abnormal absorption of electromagnetic waves and the like, and is mainly used for conductive materials (electric brushes, carbon rods and the like) and wear-resistant lubricating materials (dry powder graphite lubricants, piston cups and the like). The carbon fiber powder is a powdery carbon material obtained by secondary processing of high-strength high-modulus carbon fiber filaments with the carbon content of more than 85 percent, retains a plurality of excellent properties of carbon fibers, has small shape and large specific surface area, is easy to compound with matrix resin, can be mixed with thermoplastic resin to prepare carbon fiber reinforced thermoplastic resin injection molding materials, can be mixed with thermosetting resin (such as epoxy resin, cyanate resin, bismaleimide resin and the like) and curing agents to prepare thermosetting molding materials and casting materials, and is widely used in metal-based carbon fiber composite materials and ceramic-based carbon fiber composite materials.
Two major problems faced in the preparation and use of ultrafine powders are the crushing and dispersion of the powders. At present, the main crushing processes of carbon powder comprise mechanical crushing processes such as jet mill, vibration mill, stirring mill and the like, and dispersing is mostly carried out by adding a dispersing agent for ultrasonic dispersion, mechanical dispersion, chemical dispersion and the like. However, the ultrafine grinding technology has long process flow, complex process period and large equipment investment, and can greatly destroy the integrity of the crystal structure of graphite or carbon fiber, and reduce the performances of lubrication, heat conduction, electric conduction and the like. In addition, the ultrafine powder is easy to agglomerate in the using process, for example, when the ultrafine powder is added into copper powder to prepare a graphite/copper composite material, the ultrafine graphite powder is spontaneously aggregated in the mixing process, so that the distribution is not uniform.
Chinese patent CN 105088421B discloses a method for preparing carbon fiber powder, which mainly solves the problems of high energy consumption and low production efficiency in the prior art, and the method for preparing carbon fiber powder adopted in the invention comprises the following steps: (1) shearing, grinding and mixing continuous carbon fibers and thermoplastic resin in a molten state to obtain a mixture of carbon fiber-containing powder and the thermoplastic resin; (2) dissolving the thermoplastic resin in the mixture with a good solvent for the thermoplastic resin; (3) the technical scheme for obtaining the carbon fiber powder through solid-liquid separation better solves the technical problem and can be used in the industrial production of the carbon fiber powder.
Chinese patent CN 104098081B discloses a preparation process of carbon fiber powder with small length-diameter ratio, which comprises the following steps: A. bundling; B. bonding; C. slicing or grinding; D. dissolving; E. separating; F. and (5) purifying. The invention provides a preparation process of carbon fiber powder with small length-diameter ratio, creates a brand new production process, can produce carbon fiber powder with smaller length-diameter ratio and fineness, further can greatly improve the use effect of the carbon fiber powder, and promotes the development of industries and enterprises.
In order to solve the problem of agglomeration of carbon fiber powder, Chinese patent CN 104088132B discloses a carbon fiber powder surface modification method, which comprises the steps of firstly carrying out air firing pretreatment on carbon fiber powder, then immersing the pretreated carbon fiber powder into an oxidizing solution for surface modification, and finally carrying out cleaning treatment on the modified carbon fiber powder to obtain the surface-modified carbon fiber powder.
Japanese patent JPH10273882A discloses a method for preparing carbon fiber powder from polyacrylonitrile-based carbon fiber, which comprises slowly passing polyacrylonitrile-based carbon fiber through an oven heated to 600-700 ℃ (the pass time is 0.5-8 minutes according to the surface density of the carbon fiber) to remove sizing agent on the carbon fiber (otherwise, the carbon fiber is easy to bond when being crushed), and then cutting, crushing, and (repeatedly) grinding to obtain carbon fiber powder, wherein the length of the carbon fiber powder is generally 3-300 μm, but the carbon fiber powder obtained in the patent has wide particle size distribution, large particle size and poor hardness, and is not suitable for being used as a reinforcing material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the superfine carbon powder and the preparation method and the application thereof.
The invention relates to superfine carbon powder, which is soft superfine carbon powder, hard superfine carbon powder and superfine carbon powder embedded in metal powder, wherein the soft superfine carbon powder and the hard superfine carbon powder are obtained by crushing degummed carbon fibers through mechanical force under the assistance of the metal powder; the metal powder is not a cemented carbide powder.
The section of the hard ultrafine carbon powder is polygonal; the number of the polygonal edges is more than or equal to 4, and the particle size of the hard ultrafine carbon powder is 1-3 mu m.
In the invention, the soft ultrafine carbon powder and the hard ultrafine carbon powder have no difference in particle size, but have certain difference in hardness and graphitization degree, wherein the soft ultrafine carbon powder has higher graphitization degree, lower hardness and soft property compared with the hard ultrafine carbon powder. This is because the degummed carbon fiber has a sheath-core structure, and since the carbon fiber has a sheath layer with a higher and more distinct graphitization degree than the core, the hardness is softer, but the graphite has more distinct characteristics, such as lubricity; the core is hard in hardness, but graphite is weak in properties. Therefore, the corresponding soft superfine carbon powder is formed by crushing the carbon fiber skin layer, the property is slightly soft, the graphitization degree is higher, most of the hard superfine carbon powder is formed by crushing the carbon fiber core part, the property is hard, and the graphitization degree is slightly low.
The superfine carbon powder provided by the invention is obtained by crushing degummed carbon fibers through mechanical force, and the metal powder is added for assistance in crushing, so that the particle size distribution of the superfine carbon powder is effectively controlled, and the obtained superfine carbon powder has uniform particle size, narrow particle size distribution and good dispersibility; meanwhile, the soft superfine carbon powder and the hard superfine carbon powder both keep the microscopic crystal structure of the carbon fiber, so the carbon fiber has the excellent characteristics of strength, high conductivity, oxidation resistance and the like.
The invention relates to superfine carbon powder, which is soft metal powder, wherein the soft metal is at least one selected from silver, aluminum, copper, titanium, iron, manganese, cobalt, nickel and chromium.
Preferably, the soft metal is at least one selected from copper, iron and nickel.
The invention relates to a preparation method of superfine carbon powder; comprises the following steps of (a) carrying out,
ball-milling the degummed short carbon fiber and the soft metal powder to obtain mixed powder, and separating the mixed powder to obtain soft superfine carbon powder, hard superfine carbon powder and superfine carbon powder embedded in the metal powder;
the rotating speed of the ball milling is 220-350 r/min; the ball milling time is more than or equal to 6 h;
the mass ratio of the sum of the mass of the degummed short fibers and the soft metal powder to the mass of the ball grinding balls is 1: 5-8;
the volume ratio of the soft metal powder to the degummed short carbon fiber is 2-19: 1-3.
According to the technical scheme, the degummed short carbon fibers are subjected to ball milling by taking soft metal as a soft ball milling medium, and the superfine carbon fibers can be well realized by matching the ball milling rotating speed and the ball-to-material ratio, so that soft superfine carbon powder and hard superfine carbon powder which are uniform in particle size, narrow in distribution and retain the microstructure of the carbon fibers are obtained.
In a preferable scheme, the mass ratio of the sum of the mass of the degummed short fibers and the soft metal powder to the mass of the ball grinding balls is 1: 6-7.
The inventor finds that if unglued short carbon fibers are adopted, soft metal is not added or the rotation speed of ball milling is too high or too low, the soft superfine carbon powder and the hard superfine carbon powder with the required particle size and the required structure can not be obtained.
In a preferred scheme, the degummed short carbon fiber has the diameter of 6-8 mu m and the length of 1-4 mm.
Further preferably, the degummed short carbon fiber has a diameter of 6-7 μm and a length of 2-3 mm.
The inventor finds that the length of the degummed short carbon fiber also has certain influence on the structure of the finally obtained superfine carbon powder, the fiber is too long and is easy to wind and agglomerate during ball milling, the fiber is too short, short fibers are gathered together, and the difficulty is increased for separation.
In a preferable scheme, the particle size of the soft metal is 30-250 μm.
More preferably, the particle size of the soft metal is 100 to 150 μm.
In a preferable scheme, the rotating speed of the ball milling is 250-300 r/min; the ball milling time is 6-14 h.
Preferably, the ball milling balls are at least one selected from stainless steel balls, hard alloy balls and tungsten alloy balls.
Preferably, the diameter of the ball grinding ball is 3 mm-10 mm.
Further preferably, the diameter of the ball grinding ball is 3mm to 9 mm.
Further preferably, the ball milling balls are added according to the following mixture ratio according to the diameter of the ball milling balls, and the mixture ratio is calculated according to the mass ratio: 3mm:4mm:5mm:6mm:7mm:8mm:9 mm: 3-5: 7-9: 10-12: 18-22: 10-14: 7-9: 5-7: 1-2.
Preferably, the separation process comprises the following steps:
1) sieving the mixed powder with a 400-600-mesh sieve to obtain an oversize product A and an undersize product B, wherein the undersize product B is first-grade soft superfine carbon powder; the particle size of the first-grade soft superfine carbon powder is 1-3 mu m;
2) adding the oversize product A obtained in the step 1 into alcohol to obtain a mixed solution, carrying out ultrasonic treatment for 10-30 min, carrying out vacuum drying on the mixed solution to obtain a dried powder M, and sieving the dried powder M with a 400-600-mesh sieve to obtain an oversize product C and an undersize product D, wherein the undersize product D is second-stage soft superfine carbon powder; the grain size of the second-stage soft superfine carbon powder is 1-3 mu m;
3) and (3) carrying out heat treatment on the oversize product C obtained in the step (2) at the temperature of 150-300 ℃ for 30-60 min under a vacuum condition, then placing the oversize product C in liquid nitrogen for heat preservation treatment for 5-10 min, adding the treated oversize product C into alcohol to obtain slurry, carrying out ultrasonic treatment for 10-30 min, carrying out vacuum drying on the slurry to obtain dried powder N, sieving the dried powder N by a sieve of 400-600 meshes to obtain an oversize product E and an undersize product F, wherein the obtained undersize product F is hard superfine carbon powder, the oversize product E is superfine carbon powder embedded in metal powder, and the grain size of the superfine carbon powder embedded in the metal powder is 1-3 mu m.
Preferably, the 400-600 mesh sieve in step 1), step 2) and step 3) is selected from any one of an ultrasonic stainless steel vibrating sieve, an ultrasonic rotary vibrating sieve for ultra-fine powder separation and a common vibrating sieve.
Further preferably, the temperature of the vacuum drying in the step 2) and the step 3) is 60 to 80 ℃.
Carbon fibers are microcrystalline graphite materials obtained by stacking organic fibers such as flaky graphite microcrystals in the axial direction of the fibers and subjecting the fibers to carbonization and graphitization, and therefore have the characteristics of softness at the outside and rigidity at the inside. In the ball-milling process, the carbon fiber that comes unstuck centre gripping earlier between soft metal powder, and is broken again, broken in-process, the soft carbon layer on carbon fiber top layer is preferred broken, and in the part entered into the ball-milling jar, the remainder still remained in soft metal powder, participated further broken and inlayed, and inside stereoplasm carbon layer is then inlayed always between soft metal powder, constantly broken. Therefore, one part of the soft ultrafine carbon powder finally obtained is remained in the ball milling tank, the other part is bonded on the surface of the soft metal powder, and the hard ultrafine carbon powder is only embedded on the surface of the soft metal powder and embedded in the metal powder.
The soft or hard superfine carbon powder in the invention keeps the structure similar to carbon fiber. The soft metal powder has a particle size far larger than that of the superfine carbon powder, the soft superfine carbon powder left in the ball milling tank can be obtained by directly screening, the obtained soft superfine carbon powder is the first-stage soft superfine carbon powder, the soft superfine carbon powder bonded on the surface of the soft metal can be obtained by combining ultrasonic vibration and ultrasonic screening, the obtained soft superfine carbon powder is the second-stage soft superfine carbon powder, and the hard superfine carbon powder embedded on the surface of the soft metal needs to be obtained by combining ultrasonic vibration and ultrasonic screening after thermal expansion and cold contraction treatment by utilizing the huge difference of thermal expansion coefficients between graphite and metal powder.
In a preferred scheme, the preparation method of the degummed short carbon fiber comprises the following steps: and (3) keeping the short carbon fiber bundle at 650-800 ℃ for 20-90 min under vacuum or protective atmosphere to obtain the degummed short carbon fiber.
Preferably, the short carbon fiber bundle is subjected to heat preservation at 700-800 ℃ for 30-60 min in vacuum or nitrogen atmosphere to obtain the degummed short carbon fiber.
In the technical scheme of the invention, the length of the degummed short carbon fiber is consistent with the diameter and the length of the carbon fiber monofilament in the short carbon fiber bundle.
The inventor finds that the degumming temperature has certain influence on the performance of the final material, and the superfine carbon powder with a myopia carbon fiber structure cannot be obtained when the degumming temperature is too high or too low.
The invention relates to superfine carbon powder, which is prepared by annealing soft superfine carbon powder.
The soft superfine carbon powder is not completely graphitized, and the graphitization degree of the soft superfine carbon powder can be further improved and the hardness of the powder can be reduced by high-temperature annealing treatment.
In a preferred scheme, the annealing temperature is 650-1000 ℃, and the annealing time is 5-30 min.
Preferably, the annealing atmosphere is vacuum or protective atmosphere.
The invention relates to application of superfine carbon powder, which is used for preparing a carbon particle reinforced metal matrix composite material by embedding the superfine carbon powder in metal powder.
The superfine carbon powder designed and prepared by the invention has the granularity of only 1-3 mu m, and has narrow granularity distribution, high purity and complete structure similar to carbon fiber, so the superfine carbon powder keeps the excellent characteristics of high heat conductivity, high wear resistance, oxidation resistance and the like of the carbon fiber.
Principle and advantages:
(1) raw material selection: the short carbon fiber is adopted as a raw material, and 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, and the fibers are easy to agglomerate and cannot be crushed, so that the problem can be avoided by selecting the short carbon fiber.
(2) The short carbon fiber treatment method comprises the following steps: degumming and ball milling. 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.
The short carbon fiber is not subjected to degumming treatment, or the degumming treatment temperature is too high, or the high-energy ball milling rotating speed is too fast or too slow, or hard metal powder is selected, or the unsuitable ball-to-material ratio is not suitable, so that the preparation of the superfine carbon powder similar to the carbon fiber structure cannot be realized.
(3) The invention adopts soft metal to assist ball milling, and the carbon fiber is a microcrystalline graphite material which is formed by piling up organic fibers such as flake graphite microcrystals along the axial direction of the fiber and is obtained by carbonization and graphitization treatment, thus having the characteristics of soft outside and rigid inside. In the ball-milling process, the carbon fiber that comes unstuck centre gripping earlier between soft metal powder, and is broken again, broken in-process, the soft carbon layer on carbon fiber top layer is preferred broken, and in the part entered into the ball-milling jar, the remainder still remained in soft metal powder, participated further broken and inlayed, and inside stereoplasm carbon layer is then inlayed always between soft metal powder, constantly broken. Therefore, one part of the soft ultrafine carbon powder finally obtained is remained in the ball milling tank, the other part is embedded on the surface of the soft metal powder, and the hard ultrafine carbon powder is only embedded on the surface of the soft metal powder and in the embedded powder.
The superfine carbon powder prepared by the invention keeps the structure similar to carbon fiber no matter the superfine carbon powder is soft or hard. The soft ultrafine carbon powder remained on the ball milling tank can be obtained by directly screening (the particle size of the soft metal powder is far larger than that of the ultrafine carbon powder), the soft ultrafine carbon powder bonded on the surface of the soft metal can be obtained by combining ultrasonic vibration with ultrasonic screening, and the hard ultrafine carbon powder embedded on the surface of the soft metal can be obtained by combining ultrasonic vibration and ultrasonic screening after the metal powder is subjected to thermal expansion and cold contraction treatment.
In the invention, soft metal powder is added in the ball milling process for assistance, so that the particle size distribution of the obtained soft ultrafine carbon powder and hard ultrafine carbon powder can be effectively controlled, and the ultrafine carbon powder embedded in the metal powder can be obtained, wherein the soft and hard ultrafine carbon powder has almost all the excellent characteristics of carbon fiber, such as high hardness, high conductivity, high temperature resistance and the like, so that the prepared material has good lubricating property, conductivity, high temperature resistance and the like, can be applied to the industrial production fields including lubrication, conductivity, metallurgy, refractory materials and the like, such as graphite brushes, pure graphite pantograph, conductive coating, battery cathode materials and the like, and has the performance far superior to that of the existing composite material products taking fine graphite powder as a raw material. And compared with the existing fine graphite powder, the preparation process is simpler and the cost is lower. In addition, the soft superfine carbon powder and the hard superfine carbon powder can be directly used in different fields according to the use requirements, for example, the graphite for the carbon sliding plate is taken as an example, in order to improve the hardness and the shock resistance of the material, the hard superfine carbon powder can be selected, the use effect is far superior to that of the superfine graphite powder in the prior art, and the existing graphite powder has high graphite degree, good conductivity and lubricity, but lower hardness and is not wear-resistant. If the conductive paint or graphite brush has high requirements on conductivity and lubricating property, the soft graphite powder obtained by annealing treatment of soft carbon powder can be adopted. The superfine carbon powder embedded in the metal powder obtained by the invention is applied to be integrated with the metal powder as a whole because the metal powder is outside and the carbon powder is inside,
the method is directly used for preparing the metal composite material embedded with the carbon particles, the composite material with uniformly distributed flat particles and uniform performance is obtained through a pressing-sintering process, and the problems that carbon fibers or carbon powder are easy to agglomerate and are seriously and unevenly distributed in a metal matrix in the mixing process are solved.
In summary, the invention uses short carbon fiber as raw material, combines soft metal powder, adopts degumming treatment combined with proper high-energy ball milling raw material and process and subsequent separation process, not only obtains superfine carbon powder with complete structure and similar to carbon fiber, but also separates soft superfine carbon powder, hard superfine carbon powder and superfine carbon powder embedded in metal powder, thereby fully exerting the advantages of the three types of powder, and in addition, the soft superfine carbon powder can be graphitized to obtain soft superfine graphite powder with high graphitization degree, thus obtaining wider application. In addition, by controlling the content of the carbon fiber, a large amount of soft metal with hard ultrafine carbon powder (volume fraction is more than 90%) embedded inside can be obtained, and then the inside is oxidized by subsequent aerobic high-temperature annealing, so that porous metal powder can be obtained.
The invention firstly tries to prepare the superfine carbon powder by adopting the short carbon fiber prepared by the degumming treatment process and matching the high-energy ball milling with proper ball milling parameters with the added soft metal particle size distribution control agent.
Drawings
FIG. 1 is a flow chart of the preparation of ultrafine carbon powder according to the present invention;
FIG. 2 is a powder SEM morphology obtained by directly subjecting commercially available short carbon fibers to high energy ball milling in comparative example 1;
FIG. 3 is a powder SEM morphology obtained by high-energy ball milling of 1000 ℃ degummed short carbon fiber in comparative example 2;
FIG. 4 shows that the short carbon fiber degummed at 700 ℃ was passed too high (600r/min) in comparative example 3.
FIG. 5 is a powder SEM morphology prepared by degumming short carbon fibers at 700 ℃ in example 1 at 250r/min with a high energy ball milling method in combination with an annealing treatment at 800 ℃;
FIG. 6 is a Raman spectrum of powder prepared by using a short carbon fiber 250r/min high-energy ball milling method subjected to degumming treatment at 700 ℃ in example 1 and combining annealing treatment at 800 ℃; in the figure, from top to bottom, superfine carbon powder, carbon fiber and degummed carbon fiber are sequentially arranged;
FIG. 7 is a powder particle size distribution curve prepared by the 700 ℃ degummed short carbon fiber 250r/min high energy ball milling method in example 1 in combination with 800 ℃ annealing treatment.
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.
Example 1
In example 1, a commercially available short carbon fiber was used, and the diameter of the commercially available short carbon fiber was 7 μm and the length thereof was 2 mm. Keeping the temperature at 700 ℃ for 60min under the vacuum condition, and carrying out degumming treatment; then adding the electrolytic copper powder into ball milling equipment together for high-energy ball milling, wherein the particle size of the added electrolytic copper powder is 100 mu m; the volume ratio of the electrolytic copper powder to the degummed short carbon fiber is 4: 1, the ball milling rotation speed is 250r/min, the ball milling time is 6 hours, the ball milling ball is a stainless steel ball, the ball diameter is 3 mm-10 mm (the mass ratio of the ball milling ball diameter is 3mm, 4mm, 5mm, 6mm, 7mm, 8mm and 9mm is 4:8:11:20:12:8:6:1), and the mass ratio of the sum of the mass of the degummed short fibers and the electrolytic copper powder to the ball milling ball is 1: 6.
After the ball milling is finished, collecting the powder in the ball milling tank, and then picking out the ball milling balls for separation. Step 1, placing the mixed powder on an ultra-fine powder separation ultrasonic rotary vibration sieve for sieving treatment, wherein the minimum mesh number of the sieve is 400 meshes, and reserving undersize products, namely first-grade soft ultra-fine carbon powder. And 2, mixing oversize products, namely copper powder with the surface embedded with the superfine carbon powder, with alcohol, performing ultrasonic treatment for 20min, maintaining the temperature of the solution at room temperature, performing vacuum drying on the ultrasonic solution at 60 ℃ to obtain soft superfine carbon powder and copper powder with hard superfine carbon powder left on the surface, further performing screening through an ultrasonic rotary vibration screen for separating the superfine powder, wherein the minimum mesh number of the screen is 400 meshes, and keeping undersize products, namely second-stage soft superfine carbon powder. And 3, directly placing copper powder with oversize, namely copper powder with hard superfine carbon powder left on the surface, preserving heat for 30min at 150 ℃, directly placing the copper powder in liquid nitrogen, preserving heat for 10min, mixing the copper powder with alcohol, carrying out ultrasonic treatment for 20min, carrying out vacuum drying on the ultrasonic solution at 60 ℃ to obtain hard superfine carbon powder and superfine carbon powder embedded in electrolytic copper powder, and further carrying out screening treatment by using a superfine powder separation ultrasonic rotary vibration screen, wherein the minimum mesh number of the screen is 400 meshes, the undersize is hard superfine carbon powder, and the oversize is superfine carbon powder embedded in the electrolytic copper powder.
The morphology of the ultrafine carbon powder (mixture of primary and secondary soft ultrafine carbon powder and hard ultrafine carbon powder) obtained in this example 1 is shown in fig. 5, and it can be known from the figure that the original short carbon fiber bundle is broken into particles with a particle size of about 1-3 μm by degumming treatment in combination with soft metal powder and a suitable high-energy ball milling process.
The raman spectrum of the ultrafine carbon powder obtained in this example 1 is shown in fig. 6, and raman spectrum analysis shows that the particle structure shown in fig. 5 is similar to the carbon fiber structure, and the structural defects are slightly increased.
The particle size distribution curve of the ultrafine carbon powder obtained in this example 1 is shown in fig. 7, the particle size is 1 to 3 μm, and the particle size distribution is narrow and symmetrical.
Application example 1
The superfine carbon powder embedded in the electrolytic copper powder obtained in the embodiment 1 is applied to preparing the superfine carbon particle reinforced copper-based composite material, wherein the superfine carbon powder embedded in the electrolytic copper powder and the electrolytic copper powder are used as a whole when being applied, the electrolytic copper powder finally forms a copper matrix, and the superfine carbon powder forms a reinforcement. In the following mass ratio, the mass of the ultrafine carbon powder embedded in the electrolytic copper powder means the total mass of the ultrafine carbon powder and the electrolytic copper powder.
The superfine carbon powder embedded in the electrolytic copper powder obtained in the example 1 is embedded in the electrolytic copper powder, the particle size of the external electrolytic copper powder is 120 μm, and the superfine carbon powder is prepared from the following components in percentage by mass: 99.0 percent of superfine carbon powder and 1 percent of silicon carbide which are embedded in the electrolytic copper powder are mixed in a V-shaped mixer to obtain mixed powder. Wherein the grain diameter of the prepared silicon carbide is 100 mu m. And (3) carrying out cold pressing on the obtained mixed powder at room temperature, wherein the pressing pressure is 450MPa, the pressure maintaining time is 20s, the prepared copper-based composite material pressed compact is subjected to pressure sintering under the protection of hydrogen atmosphere, the copper-based composite material pressed compact is sintered for 2h at 950 ℃, the heating rate and the cooling rate of a furnace are both 12 ℃/min, and the pressure is 0.85MPa, so that the superfine carbon particle reinforced copper-based composite material is obtained. The density of the copper-based composite material is 98.3%, and the bending strength is 827 MPa.
Example 2
In example 2, a commercially available short carbon fiber was used, and the diameter of the commercially available short carbon fiber was 6 μm and the length thereof was 2 mm. Keeping the temperature at 800 ℃ for 30min under the protection of nitrogen, and degumming; then adding the powder and reduced iron powder into ball milling equipment for high-energy ball milling, wherein the particle size of the added reduced iron powder is 150 mu m; the volume ratio of the reduced iron powder to the degummed short carbon fiber is 2: 3, the ball milling rotation speed is 300r/min, the ball milling time is 6 hours, the ball milling balls are stainless steel balls and hard alloy balls, the ball diameter is 3 mm-10 mm (the mass ratio of the ball milling ball diameter of 3mm, 4mm, 5mm, 6mm, 7mm, 8mm and 9mm is 4:8:11:20:12:8:6:1), and the mass ratio of the sum of the mass of the degummed short fibers and the reduced iron powder to the ball milling balls is 1: 7.
After the ball milling is finished, collecting the powder in the ball milling tank, and then picking out the ball milling balls for separation. Step 1, placing the mixed powder on an ultra-fine powder separation ultrasonic rotary vibration sieve for sieving treatment, wherein the minimum mesh number of the sieve is 500 meshes, and reserving undersize products, namely first-grade soft ultra-fine carbon powder. And 2, mixing oversize products, namely iron powder with the surface embedded with superfine carbon powder, with alcohol, performing ultrasonic treatment for 20min, maintaining the temperature of the solution at room temperature, performing vacuum drying on the ultrasonic solution at 60 ℃ to obtain soft superfine carbon powder and iron powder with hard superfine carbon powder left on the surface, further performing screening by using a superfine powder separation ultrasonic rotary vibration screen, wherein the minimum mesh number of the screen is 500 meshes, and keeping undersize products, namely second-stage soft superfine carbon powder. And 3, directly placing the oversize product, namely the iron powder with the hard superfine carbon powder left on the surface, in liquid nitrogen for 10min after vacuum heat preservation at 150 ℃, mixing with alcohol, performing ultrasonic treatment for 20min, performing vacuum drying on the ultrasonic solution at 60 ℃ to obtain the hard superfine carbon powder and the iron powder with the hard superfine carbon powder left inside, and further performing screening treatment by using a superfine powder separation ultrasonic rotary vibration screen, wherein the minimum mesh number of the screen is 500 meshes, the undersize product is the hard superfine carbon powder, and the oversize product is the superfine carbon powder embedded inside the iron powder.
The structure of the ultrafine carbon powder (the first-stage and second-stage soft ultrafine carbon powders and the hard ultrafine carbon powder are collectively called) obtained in this example 2 is similar to that of carbon fiber, and the particle size is 1 to 3 μm.
Application example 2
The ultrafine carbon powder embedded in the iron powder obtained in the embodiment 2 is applied to the preparation of the ultrafine carbon particle reinforced iron-based composite material, wherein the ultrafine carbon powder embedded in the iron powder is integrated with the iron powder when applied, the iron powder finally forms a copper matrix, and the ultrafine carbon powder forms a reinforcement.
And (2) carrying out cold pressing on the superfine carbon powder with the particle size of 180 microns embedded in the iron powder obtained in the example 2 at room temperature, wherein the pressing pressure is 550MPa, the pressure maintaining time is 20s, the prepared iron alloy green compact is subjected to pressure sintering under the vacuum protection, is sintered for 2h at 750 ℃, is heated to 1100 ℃ and is sintered for 2h, and the heating rate and the cooling rate of a furnace are both 10-15 ℃/min, and the pressure is 0.45MPa, so as to obtain the superfine iron carbide particle reinforced iron alloy. The density of the iron alloy is 98.5%, and the tensile strength is 750 MPa.
Example 3
In example 3, commercially available short carbon fibers having a diameter of 6 μm and a length of 1mm were used. Keeping the temperature at 700 ℃ for 30min under the vacuum condition, and carrying out degumming treatment; then adding the mixture and electrolytic nickel powder into ball milling equipment for high-energy ball milling, wherein the particle size of the added electrolytic nickel powder is 100 mu m; the volume ratio of the electrolytic nickel powder to the degummed short carbon fiber is 19:1, the ball milling rotation speed is 250r/min, the ball milling time is 14h, the ball milling balls are stainless steel balls and hard alloy balls, the ball diameter is 3 mm-10 mm (the mass ratio of the ball milling ball diameter of 3mm, 4mm, 5mm, 6mm, 7mm, 8mm and 9mm is 4:8:11:20:12:8:6:1), and the mass ratio of the sum of the mass of the degummed short fibers and the electrolytic nickel powder to the ball milling balls is 1: 7.
After the ball milling is finished, collecting the powder in the ball milling tank, and then picking out the ball milling balls for separation. Step 1, placing the mixed powder on an ultra-fine powder separation ultrasonic rotary vibration sieve for sieving treatment, wherein the minimum mesh number of the sieve is 500 meshes, and reserving undersize products, namely first-grade soft ultra-fine carbon powder. And 2, mixing the nickel powder with the ultrafine carbon powder embedded on the surface of the oversize product with alcohol, performing ultrasonic treatment for 20min, maintaining the temperature of the solution at room temperature, performing vacuum drying on the ultrasonic solution at 60 ℃ to obtain soft ultrafine carbon powder and nickel powder with hard ultrafine carbon powder left on the surface, further performing screening by using an ultrafine powder separation ultrasonic rotary vibration screen, wherein the minimum mesh number of the screen is 500 meshes, and keeping the undersize product, namely the second-stage soft ultrafine carbon powder. And 3, directly placing the nickel powder with the oversize, namely the nickel powder with the hard ultrafine carbon powder left on the surface in liquid nitrogen for heat preservation for 10min after vacuum heat preservation at 150 ℃, mixing with alcohol, performing ultrasonic treatment for 20min, performing vacuum drying on the ultrasonic solution at 60 ℃ to obtain the hard ultrafine carbon powder and the nickel powder with the hard ultrafine carbon powder left inside, and further performing screening treatment by an ultrafine powder separation ultrasonic rotary vibration screen, wherein the minimum mesh number of the screen is 500 meshes, the undersize is the hard ultrafine carbon powder, and the oversize is the ultrafine carbon powder embedded inside the nickel powder.
The structure of the ultrafine carbon powder (the first-stage and second-stage soft ultrafine carbon powders and the hard ultrafine carbon powder are collectively called) obtained in this embodiment 3 is similar to that of carbon fiber, and the particle size is 1 to 3 μm.
Application example 3
The ultrafine carbon powder embedded in the nickel powder obtained in the embodiment 3 is applied to the preparation of the ultrafine carbon particle reinforced nickel-based composite material, wherein the ultrafine carbon powder embedded in the nickel powder and the nickel powder are taken as a whole when being applied, the nickel powder finally forms a nickel matrix, and the ultrafine carbon powder forms a reinforcement body. In the following mass ratio, the mass of the ultrafine carbon powder embedded in the nickel powder refers to the total mass of the ultrafine carbon powder and the nickel powder.
And (2) embedding the superfine carbon powder obtained in the embodiment 3 into the nickel powder, wherein the particle size of the nickel powder is 180 μm, and the nickel powder comprises the following components in percentage by mass: 96.0 percent of ultrafine carbon powder and 4 percent of aluminum oxide which are embedded in the nickel powder are mixed in a V-shaped mixer to obtain mixed powder. Wherein the grain diameter of the prepared alumina is 120 μm. And (3) cold pressing the obtained mixed powder at room temperature, wherein the pressing pressure is 450MPa, the pressure maintaining time is 20s, the prepared nickel-based composite material pressed compact is subjected to pressure sintering under the protection of hydrogen atmosphere, the pressed compact is sintered for 2 hours at 1000 ℃, the heating rate and the cooling rate of a furnace are both 10-15 ℃/min, and the pressure is 0.5MPa, so that the superfine carbon particle reinforced nickel-based composite material is obtained. The density of the nickel-based composite material is 98.2%, and the tensile strength is 1450 MPa.
Comparative example 1
Other conditions of the comparative example 1 are the same as those of the example 1, only the commercially available short carbon fibers are directly used as objects, the commercially available short carbon fibers are added into ball milling equipment for high-energy ball milling without any pretreatment, the rotating speed is 250r/min, the ball milling time is 6 hours, ball milling balls are stainless steel balls, the ball diameter is 3 mm-10 mm, the ball milling balls are added according to a certain proportion (the mass ratio of the ball milling ball diameter to the ball milling ball diameter is 4:8:11:20:12:8:6:1, the mass ratio of the sum of the mass of the degummed short fibers and the mass of the soft metal powder to the ball milling ball is 1: 6). The short carbon fibers are not broken and are adhered to the wall of the ball milling pot, and the appearance of the treated fibers is shown in figure 2.
Comparative example 2
Comparative example 2 the other conditions were the same as in example 1 except that the degumming temperature was 1000 ℃. The method comprises the steps of taking commercially available short carbon fibers as objects, degumming at 1000 ℃, adding the short carbon fibers into ball milling equipment for high-energy ball milling at the rotating speed of 250r/min for 6h, wherein ball-milled balls are stainless steel balls, the ball diameters of the balls are 3-10 mm, the ball milling balls are added according to a certain ratio (the mass ratio of the ball-milled balls to the diameters of 3mm, 4mm, 5mm, 6mm, 7mm, 8mm and 9mm is 4:8:11:20:12:8:6:1), and the mass ratio of the sum of the mass of the degummed short fibers and the mass of the soft metal powder to the ball-milled balls is 1: 6. The short carbon fibers were not significantly broken, and the morphology of the treated fibers is shown in FIG. 3.
Comparative example 3
Other conditions of this comparative example 3 were the same as those of example 1 except that the ball milling rotation speed was 600 r/min. The method comprises the steps of taking commercially available short carbon fibers as objects, degumming at 700 ℃, adding the short carbon fibers into ball milling equipment for high-energy ball milling at the rotating speed of 600r/min for 6h, wherein ball-milled balls are stainless steel balls, the ball diameters of the balls are 3-10 mm, the ball milling balls are added according to a certain ratio (the mass ratio of the ball-milled balls to the diameters of 3mm, 4mm, 5mm, 6mm, 7mm, 8mm and 9mm is 4:8:11:20:12:8:6:1), and the mass ratio of the sum of the mass of the degummed short fibers and the mass of the soft metal powder to the ball-milled balls is 1: 6. The short carbon fibers did not break down significantly, most deposited on the top lid of the ball mill pot, and the morphology of the treated fibers is shown in FIG. 4.
Comparative example 4
Other conditions of the comparative example 4 are the same as those of the example 1, only electrolytic copper powder is not added in the ball milling process, only the commercially available short carbon fiber is taken as an object, and the temperature is kept for 60min at 700 ℃ under the vacuum condition for degumming treatment; and then adding the mixture into ball milling equipment for high-energy ball milling, wherein the rotating speed is 250r/min, the ball milling time is 6 hours, the ball milling ball is a stainless steel ball, and the mass ratio of the sum of the mass of the degummed short fibers and the mass of the soft metal powder to the ball milling ball is 1: 6. The carbon fibers are agglomerated into lumps without being broken.
From the comparative examples and the topographical maps 2 to 4 described above; the short carbon fiber is not subjected to special carbonization treatment, or the carbonization treatment temperature is too high, no soft metal is added in the ball milling process, or the high-energy ball milling rotating speed is too high or too low, or the subsequent annealing treatment is not performed, so that the superfine carbon powder similar to the carbon fiber structure cannot be realized.
Comparative example 5
Other conditions were the same as in example 1, except that the commercially available short carbon fiber had a diameter of 7 μm and a length of 10 mm. Keeping the temperature at 700 ℃ for 60min under the vacuum condition, and carrying out degumming treatment; then adding the electrolytic copper powder into ball milling equipment together for high-energy ball milling, wherein the particle size of the added electrolytic copper powder is 150 mu m; the volume ratio of the electrolytic copper powder to the degummed short carbon fiber is 2: 3, the ball milling rotation speed is 250r/min, the ball milling time is 6 hours, the ball milling ball is a stainless steel ball, the ball diameter is 3 mm-10 mm (the mass ratio of the ball milling ball diameter is 3mm, 4mm, 5mm, 6mm, 7mm, 8mm and 9mm is 4:8:11:20:12:8:6:1), and the mass ratio of the sum of the mass of the degummed short fibers and the electrolytic copper powder to the ball milling ball is 1: 6. Because the short carbon fiber is too long, the carbon fiber is too long after 6 hours of ball milling, and is agglomerated into a ball without being broken.
Comparative example 6
Other conditions were the same as in example 1, except that the commercially available short carbon fiber had a diameter of 7 μm and a length of 1 mm. Keeping the temperature at 700 ℃ for 60min under the vacuum condition, and carrying out degumming treatment; then adding the electrolytic copper powder into ball milling equipment together for high-energy ball milling, wherein the particle size of the added electrolytic copper powder is 150 mu m; the volume ratio of the electrolytic copper powder to the degummed short carbon fiber is 25: 1, the ball milling rotation speed is 250r/min, the ball milling time is 6 hours, the ball milling ball is a stainless steel ball, the ball diameter is 3 mm-10 mm (the mass ratio of the ball milling ball diameter is 3mm, 4mm, 5mm, 6mm, 7mm, 8mm and 9mm is 4:8:11:20:12:8:6:1), and the mass ratio of the sum of the mass of the degummed short fibers and the electrolytic copper powder to the ball milling ball is 1: 6. Due to the fact that the adding amount of the electrolytic copper powder is too high, although fibers are crushed, the superfine carbon powder separated after crushing is extremely limited. After the ball milling is finished, collecting the powder in the ball milling tank, and then picking out the ball milling balls for separation. The separation procedure was the same as in example 1. After separation, it was found that in this example, the amount of the first-grade soft ultrafine carbon powder, the second-grade soft ultrafine carbon powder, and the hard ultrafine carbon powder obtained in the final step are significantly less than those obtained in the example, because the soft metal is added in an excessive amount, and most of the carbon powder is embedded in the soft metal.
And (3) mixing the superfine carbon powder embedded in the electrolytic copper powder, which is obtained in the comparative example 6, with the particle size of 180 microns, 99.0 percent of the superfine carbon powder embedded in the electrolytic copper powder and 1 percent of silicon carbide according to mass percentage in a V-shaped mixer to obtain mixed powder. Wherein the grain diameter of the prepared silicon carbide is 200 μm. And (3) cold pressing the obtained mixed powder at room temperature, wherein the pressing pressure is 450MPa, the pressure maintaining time is 20s, the prepared copper-based composite material pressed compact is subjected to pressure sintering under the protection of hydrogen atmosphere, the copper-based composite material pressed compact is sintered for 2h at 950 ℃, the heating rate and the cooling rate of a furnace are both 12 ℃/min, and the pressure is 0.35MPa, so that the copper-based composite material is obtained. The density of the copper-based composite material is 98 percent, and the bending strength is 480 MPa.
Comparative example 7
Other conditions were the same as in example 1, except that the commercially available short carbon fiber had a diameter of 7 μm and a length of 1 mm. Keeping the temperature at 700 ℃ for 60min under the vacuum condition, and carrying out degumming treatment; then adding the electrolytic copper powder into ball milling equipment together for high-energy ball milling, wherein the particle size of the added electrolytic copper powder is 150 mu m; the volume ratio of the electrolytic copper powder to the degummed short carbon fiber is 1: 1, the ball milling rotation speed is 250r/min, the ball milling time is 6 hours, the ball milling ball is a stainless steel ball, the ball diameter is 3 mm-10 mm (the mass ratio of the ball milling ball diameter is 3mm, 4mm, 5mm, 6mm, 7mm, 8mm and 9mm is 4:8:11:20:12:8:6:1), and the mass ratio of the sum of the mass of the degummed short fibers and the electrolytic copper powder to the ball milling ball is 1: 6.
After the ball milling is finished, collecting the powder in the ball milling tank, and then picking out the ball milling balls for separation. The separation procedure was the same as in example 1.
The addition amount of the soft metal added in the comparative example 7 is too small, so that the particle size distribution of the finally obtained primary soft ultrafine carbon powder, secondary soft ultrafine carbon powder and hard ultrafine carbon powder is widened, and part of fibers are not completely crushed.
And (3) mixing the superfine carbon powder embedded in the electrolytic copper powder, which is obtained in the comparative example 7, with the particle size of 180 microns, 99.0 percent of the superfine carbon powder embedded in the electrolytic copper powder and 1 percent of silicon carbide according to mass percentage in a V-shaped mixer to obtain mixed powder. Wherein the grain diameter of the prepared silicon carbide is 200 μm. And (3) cold pressing the obtained mixed powder at room temperature, wherein the pressing pressure is 450MPa, the pressure maintaining time is 20s, the prepared copper-based composite material pressed compact is subjected to pressure sintering under the protection of hydrogen atmosphere, the copper-based composite material pressed compact is sintered for 2h at 950 ℃, the heating rate and the cooling rate of a furnace are both 12 ℃/min, and the pressure is 0.65MPa, so that the copper-based composite material is obtained. The density of the copper-based composite material is 95%, and the bending strength is 450 MPa.
Claims (7)
1. The preparation method of the superfine carbon powder is characterized by comprising the following steps:
ball-milling the degummed short carbon fiber and the soft metal powder to obtain mixed powder, and separating the mixed powder to obtain soft superfine carbon powder, hard superfine carbon powder and superfine carbon powder embedded in the metal powder;
the rotating speed of the ball milling is 220-350 r/min; the ball milling time is more than or equal to 6 h;
the mass ratio of the sum of the mass of the degummed short fibers and the soft metal powder to the mass of the ball grinding balls is 1: 5-8;
the volume ratio of the soft metal powder to the degummed short carbon fiber is 2-19: 1-3;
the soft metal is at least one of silver, aluminum, copper, titanium, iron, manganese, cobalt, nickel and chromium;
the separation process comprises the following steps:
1) sieving the mixed powder with a 400-600-mesh sieve to obtain an oversize product A and an undersize product B, wherein the undersize product B is first-grade soft superfine carbon powder; the particle size of the first-grade soft superfine carbon powder is 1-3 mu m;
2) adding the oversize product A obtained in the step 1 into alcohol to obtain a mixed solution, carrying out ultrasonic treatment for 10-30 min, carrying out vacuum drying on the mixed solution to obtain a dried powder M, and sieving the dried powder M with a 400-600-mesh sieve to obtain an oversize product C and an undersize product D, wherein the undersize product D is second-stage soft superfine carbon powder; the grain size of the second-stage soft superfine carbon powder is 1-3 mu m;
3) and (3) carrying out heat treatment on the oversize product C obtained in the step (2) at 150-300 ℃ for 30-60 min under a vacuum condition, then placing the oversize product C in liquid nitrogen for heat preservation treatment for 5-10 min, adding the treated oversize product C into alcohol to obtain slurry, carrying out ultrasonic treatment for 10-30 min, carrying out vacuum drying on the slurry to obtain dried powder N, and sieving the dried powder N through a 400-600-mesh sieve to obtain an oversize product E and an undersize product F, wherein the obtained undersize product F is hard superfine carbon powder, the oversize product E is superfine carbon powder embedded in metal powder, and the grain size of the superfine carbon powder embedded in the metal powder is 1-3 mu m.
2. The method for preparing ultrafine carbon powder according to claim 1,
the degummed short carbon fiber has the diameter of 6-8 mu m and the length of 1-4 mm;
the particle size of the soft metal is 30-250 μm.
3. The method for preparing ultrafine carbon powder according to claim 1,
the rotating speed of the ball milling is 250-300 r/min; the ball milling time is 6-14 h;
the ball milling balls are at least one of stainless steel balls, hard alloy balls and tungsten alloy balls;
the diameter of the ball grinding ball is 3 mm-10 mm.
4. The method for preparing ultrafine carbon powder according to claim 1, wherein the degummed short carbon fiber is prepared by the following steps: and (3) keeping the short carbon fiber bundle at 650-800 ℃ for 20-90 min under vacuum or protective atmosphere to obtain the degummed short carbon fiber.
5. The method for preparing ultrafine carbon powder according to claim 1, wherein the soft ultrafine carbon powder is annealed to obtain ultrafine graphite powder; the annealing temperature is 650-1000 ℃, and the annealing time is 5-30 min.
6. The method for preparing ultrafine carbon powder according to claim 1, wherein the method comprises the following steps: the section of the hard superfine carbon powder is polygonal; the number of the polygonal edges is more than or equal to 4, and the particle size of the hard ultrafine carbon powder is 1-3 mu m.
7. The use of the ultrafine carbon powder prepared by the preparation method according to any one of claims 1 to 6, wherein: and applying the superfine carbon powder embedded in the metal powder to the preparation of the carbon particle reinforced metal matrix composite material.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910034512.2A CN109702211B (en) | 2019-01-15 | 2019-01-15 | Preparation method and application of superfine carbon powder |
| PCT/CN2019/081421 WO2020147206A1 (en) | 2019-01-15 | 2019-04-04 | Ultrafine carbon powder, preparation method therefor, and use thereof |
| JP2021540498A JP7328712B2 (en) | 2019-01-15 | 2019-04-04 | Ultrafine carbon powder and its production method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910034512.2A CN109702211B (en) | 2019-01-15 | 2019-01-15 | Preparation method and application of superfine carbon powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109702211A CN109702211A (en) | 2019-05-03 |
| CN109702211B true CN109702211B (en) | 2021-03-12 |
Family
ID=66261344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910034512.2A Active CN109702211B (en) | 2019-01-15 | 2019-01-15 | Preparation method and application of superfine carbon powder |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP7328712B2 (en) |
| CN (1) | CN109702211B (en) |
| WO (1) | WO2020147206A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113061027B (en) * | 2021-04-13 | 2022-12-13 | 矿冶科技集团有限公司 | Method for removing fine powder on surface of spherical ceramic powder, spherical ceramic powder and application |
| CN114685186A (en) * | 2022-03-25 | 2022-07-01 | 长沙诚智新材料科技有限公司 | Modified carbon fiber, modified carbon graphite material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10273882A (en) * | 1997-03-31 | 1998-10-13 | Toray Ind Inc | Milled carbon fiber and its production |
| CN103333473A (en) * | 2013-04-18 | 2013-10-02 | 邱献腾 | Composite material of carbon fibers or carbon fiber powder, and processing process thereof |
| CN106086718A (en) * | 2016-07-13 | 2016-11-09 | 宁波宏协离合器有限公司 | A kind of clutch iron base composite friction material and preparation method thereof |
| CN107747070A (en) * | 2017-11-24 | 2018-03-02 | 中南大学 | A kind of high-temperature wear-resistant composite material and preparation method thereof |
| CN108018506A (en) * | 2017-12-08 | 2018-05-11 | 湖南锴博新材料科技有限公司 | A kind of short carbon fiber is modified height and rubs composite material and its preparation method and application |
-
2019
- 2019-01-15 CN CN201910034512.2A patent/CN109702211B/en active Active
- 2019-04-04 JP JP2021540498A patent/JP7328712B2/en active Active
- 2019-04-04 WO PCT/CN2019/081421 patent/WO2020147206A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10273882A (en) * | 1997-03-31 | 1998-10-13 | Toray Ind Inc | Milled carbon fiber and its production |
| CN103333473A (en) * | 2013-04-18 | 2013-10-02 | 邱献腾 | Composite material of carbon fibers or carbon fiber powder, and processing process thereof |
| CN106086718A (en) * | 2016-07-13 | 2016-11-09 | 宁波宏协离合器有限公司 | A kind of clutch iron base composite friction material and preparation method thereof |
| CN107747070A (en) * | 2017-11-24 | 2018-03-02 | 中南大学 | A kind of high-temperature wear-resistant composite material and preparation method thereof |
| CN108018506A (en) * | 2017-12-08 | 2018-05-11 | 湖南锴博新材料科技有限公司 | A kind of short carbon fiber is modified height and rubs composite material and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109702211A (en) | 2019-05-03 |
| WO2020147206A1 (en) | 2020-07-23 |
| JP7328712B2 (en) | 2023-08-17 |
| JP2022517022A (en) | 2022-03-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109570493B (en) | Composite powder of metal-metal carbide coated carbon particles and preparation method thereof | |
| CN101892411B (en) | Novel WC-based hard alloy material and preparation method thereof | |
| CN111644615B (en) | Preparation method for realizing high strength and toughness of TC4 titanium alloy by co-strengthening method | |
| CN109487181B (en) | Aluminum oxide reinforced copper-based composite material and preparation method thereof | |
| CN109554565B (en) | Interface optimization method of carbon nanotube reinforced aluminum matrix composite | |
| CN109702211B (en) | Preparation method and application of superfine carbon powder | |
| CN109676540B (en) | Copper-based binder zirconium corundum grinding wheel for grinding railway steel rail and preparation method thereof | |
| CN109680228B (en) | Preparation method of carbon-reinforced metal-based composite material | |
| CN109695007B (en) | Preparation method of metal-carbon composite material | |
| CN105081312A (en) | Method for preparing grapheme/copper composite material by loading solid carbon source on copper powder surface in impregnation manner | |
| CN108570630B (en) | Aluminum oxide particle and whisker co-reinforced copper-based composite material and preparation method thereof | |
| CN110066972B (en) | C/C-Ni-Cu composite material and preparation method and application thereof | |
| CN108570590B (en) | Impregnated diamond matrix, impregnated diamond material and preparation method thereof | |
| CN110257738B (en) | Preparation method of superfine carbon particle reinforced metal matrix composite material | |
| CN112831733A (en) | Amorphous coated Y2O3Composite material and powder preparation method thereof | |
| CN112008087A (en) | Method for improving comprehensive performance of carbon nano material reinforced nickel-based high-temperature alloy | |
| CN106756168B (en) | The method that one kind prepares Ti (C, N) based ceramic metal based on carbon thermal reduction molybdenum trioxide | |
| CN111251199A (en) | Copper-based binder carborundum grinding wheel special for railway steel rail grinding and preparation method thereof | |
| CN109675707B (en) | Application of soft metal in preparation of superfine carbon powder | |
| CN106566972A (en) | Preparation method of plate-shaped WC crystal grain hard alloy with gradient structure | |
| CN109518032B (en) | Preparation method of carbon particle reinforced metal matrix composite material | |
| CN113526959B (en) | Method and device for rapidly sintering tungsten carbide powder without adhesive | |
| CN113751707B (en) | Method for preparing nano carbide particle dispersion strengthening alloy powder | |
| CN108531764A (en) | A kind of silver tungsten carbide carbon alkene contact material and preparation method thereof | |
| CN112091220B (en) | Polycrystalline diamond compact with good heat conduction performance and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |