JP7164906B2 - METHOD FOR PREPARATION OF METAL MATERIAL OR METAL COMPOSITE MATERIAL - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method of preparing a metallic material or metal composite material, specifically to a method of preparing a metallic material or metal composite material by adding phenol-formaldehyde resin powder.

Carbon particle (carbon fiber, graphite, etc.) reinforced metal matrix composites combine the high electrical and thermal conductivity of metal, good toughness and corrosion resistance with the high toughness and corrosion resistance of carbon fiber, and the lubricating properties of graphite. It is widely applied in fields such as conductive materials, electrical conductive materials, and friction materials.

In recent years, researchers have done a lot of research to improve the mechanical properties and high-temperature oxidation resistance performance of composites, mainly focusing on improving the wettability of the carbon/metal interface, adding carbon to For example, by plating metal on the surface of carbon or adding other alloying elements to metal, the wettability of the interface with carbon is reduced, and artificial particles and carbon fibers are used to improve the oxidation resistance performance of the material. is improved, and the coating treatment with phenol-formaldehyde resin accelerates the reduction of the metal oxide film layer and promotes the sintering diffusion of the metal.

According to Chinese invention patent CN104388847B, the ingredients are weighed and mixed by ball milling. The mixing time is 3 hours to obtain a mixed material. Step 1 in which a copper layer is plated on the surface of the graphite powder with a thickness of 50 μm by chemical plating technology, Step 2 in which the mixed material prepared in Step 1 is pressed at a pressure of 700 MPa to obtain a blank, and the above step. Step 3: secondary sintering the blank prepared in step 2 to obtain a sintered alloy block; A method of preparing a carbon fiber reinforced copper matrix composite is disclosed, comprising step 4 of obtaining a matrix composite. The copper-based composite prepared according to the present invention not only has excellent self-lubricating performance, but also has excellent wear resistance and mechanical properties. However, in this invention, the carbon fiber is mixed with nickel powder, iron powder, copper powder, etc. by ball milling, which seriously damages the carbon fiber. causes the non-uniform distribution of the carbon fiber and copper, and the decompatibility phenomenon at the interface between carbon fiber and copper is obvious, further affecting the performance of the material.

Chinese invention patent CN108441791A is composed of a carbon fiber preform, an interface layer, a ceramics matrix and a metal matrix, the metal is one of aluminum alloy, magnesium alloy, copper alloy and tin alloy, the ceramic is SiC, and this A carbon fiber reinforced metal-ceramic composite material has been disclosed in which the density of the composite material is 1.8-3.8 g/cm ³ . This patent also disclosed a method of preparing different alloy-ceramic composites. Such composites have the advantages of short preparation cycle and adjustable density, which can overcome the brittleness and low density of ceramics and meet the demand for ceramic-based composites in many fields. . However, in the present invention, the ceramic matrix is first prepared in the carbon fiber preform, and then the metal matrix is prepared to protect the carbon fiber from damage by the molten metal. The ceramic matrix is prepared in a carbon fiber preform, which inevitably damages the carbon fiber, and the resulting ceramic interfacial layer is highly brittle, adversely affecting performance.

According to research conducted by the inventors, it is possible to obtain metal powder in which carbon particles or short carbon fibers are evenly embedded by ball milling degummed carbon fibers or carbon fibers coated with phenol formaldehyde resin and soft metal. I found In Chinese invention patent CN108018506A, the raw materials used include 1-3 wt% of resin-coated short carbon fiber and 15 wt% or more of nano-oxide dispersion-strengthened copper powder. , Nano-oxide is an in-situ carbon short fiber modified high friction composite material, which is prepared by ball milling resin-coated-cured short carbon fiber and metal copper powder to prepare pre-alloy powder, and other We disclosed the preparation of short carbon fiber modified high friction composites by mixing with component powders and press sintering. However, in this method, a small amount of carbon fibers are exposed to the outside of the copper particles, which hinders sintering diffusion between the copper particles and causes a non-densification phenomenon due to sintering. For example, either plating a transition metal onto the surface of carbon, or forming a metal carbide by oxidation or soak-decomposition combination, affects the performance of the carbon particles or carbon fibers themselves. The present invention uses a combination of ultrasonic treatment and low-temperature heating-quenching process to effectively remove the carbon embedded in the surface of the metal powder. At the same time as promoting sintering between particles, it effectively protects the structure of the carbon itself and maximizes its properties.

In order to solve the technical deficiencies of existing carbon/metal composite materials with poor compactness and unfavorable performance, the present invention provides a method for preparing metal materials or metal composite materials, the purpose of which is to improve compactness. is 99% or more, and a metal material or metal composite material with excellent performance such as strength and toughness is prepared, and in particular, the denseness is 99% or more, and carbon that can ensure excellent performance such as strength and toughness / To provide a metal composite material.

The method for preparing the metal material or metal composite material of the present invention includes two schemes.

Method 1: The raw materials including metal powder and phenol-formaldehyde resin powder are uniformly mixed and press-sintered to obtain a metal material.

Method 2: Ball milling the reinforcement and matrix metal A to obtain metal powder with reinforcement embedded on the surface and inside, subjecting the metal powder with reinforcement embedded to ultrasonic treatment and low temperature heating-quenching process, After removing the reinforcing particles on the surface to obtain a preliminary material, mixing the preliminary material and phenol formaldehyde resin powder, press-sintering, or after mixing the preliminary material, phenol formaldehyde resin powder and particle phase B , press-sinter to obtain a carbon/metal composite.

In the method for preparing the metal material or metal composite material of the present invention, in method 1, the particle size of the phenol-formaldehyde resin powder is 300 μm or less, and the mass ratio of the metal powder to the phenol-formaldehyde resin powder is 98 to 99.0 μm. 5: 0.5-2.

In the method for preparing the metal material or metal composite material of the present invention, in plan 2, the particle size of the phenol-formaldehyde resin powder is 100 μm or less, preferably 10 to 80 μm.

In the method for preparing a metal material or metal composite material of the present invention, the reinforcing material is at least one selected from carbon materials and carbides.

The use of a carbon material can enhance the performance of a metal matrix composite material, but often there is an interface barrier between the carbon material and the metal phase, so the reinforcing effect of the carbon material cannot be sufficiently exhibited. Therefore, the carbon material and the matrix metal are compounded in advance, and after obtaining a metal powder in which carbon is embedded, it is pressed and sintered as it is, or mixed with another hard second phase and pressed and sintered. Although this can improve the performance of the resulting carbon-reinforced metal, the extent of the improvement is limited. As a result of in-depth research by the present inventor, the carbon material is inevitably exposed on the surface of the carbon-embedded metal powder, impeding sintering diffusion during the sintering process and causing non-densification due to sintering. I discovered for the first time that In response to this technical problem first discovered by the present invention, the present invention removes the carbon material on the surface of the carbon-embedded metal powder and mixes it by using a combination of ultrasonic treatment and low-temperature heating-quenching process. In some cases, phenol formaldehyde resin powder is added, and high-temperature decomposition during sintering creates a highly reducing atmosphere, which achieves almost complete densification during sintering. to propose.

Preferably, in the method for preparing a metallic material or metallic composite material of the present invention, the carbon material is at least one of 0-dimensional, 1-dimensional, 2-dimensional and 3-dimensional carbon materials. More preferably, the carbon material is a mixture of one or more of granular graphite, carbon fibers, and carbon particles after pulverization of carbon fibers in an arbitrary ratio. In a more preferred method, the carbon material is short carbon fibers after degumming, and the method for preparing the short carbon fibers after degumming is to heat the short carbon fiber bundle to 650 to 800° C. under a protective atmosphere. , heat treatment for 20 to 90 minutes to obtain short carbon fibers after degumming. After degumming, the short carbon fibers preferably have a length of 1-5 mm and a diameter of preferably 6-8 μm.

Preferably, in the method for preparing a metal material or metal composite material of the present invention, the carbon material is a carbon material coated with phenol-formaldehyde resin. In a more preferred method, the carbon material is short carbon fibers coated with phenol formaldehyde resin, and the short carbon fibers coated with phenol formaldehyde resin are prepared by dissolving the mixed phenol formaldehyde resin in an organic solvent. After dissolving and obtaining an alcohol saturated solution of phenol formaldehyde resin, short carbon fibers are immersed in an alcohol saturated solution of phenol formaldehyde resin at 60 to 80° C. for 1 to 2 hours, and further dried at 80 to 150° C. for 1 to 3 hours, Short carbon fibers coated with phenol formaldehyde resin are obtained. The short carbon fibers are preferably short carbon fibers after degumming. After degumming, the short carbon fibers preferably have a length of 1-5 mm and a diameter of preferably 6-8 μm.

Preferably, in the method for preparing a metal material or metal composite material of the present invention, the oxide of the matrix metal A is hardly reduced and/or reducible in a reducing atmosphere of one or more of H ₂ and CO. Preferably, the matrix metal A is at least one of aluminum, titanium, zirconium, copper, iron, nickel, chromium, manganese and silver, more preferably copper, aluminum, titanium and nickel. at least one.

Preferably, in the method for preparing a metallic material or metallic composite material of the present invention, in the process of the ultrasonic treatment,
1) The metal powder embedded with the reinforcement (including the metal powder embedded with carbon on the surface and inside) is added to alcohol to obtain a mixed solution, ultrasonically treated for 5 to 60 minutes, and the mixed solution is vacuum-dried. , to obtain a dry powder M, pass the dry powder M through a sieve of 400 to 600 mesh, and sieve the metal powder from which the reinforcement on the primary surface has been removed (including the metal powder from which the carbon on the primary surface has been removed) obtaining an entity C;
2) After heat-treating the sieved material C obtained in step 1 at 150 to 300° C. for 30 to 60 minutes under vacuum conditions, place it in liquid nitrogen and heat-treat it for 5 to 10 minutes. to obtain a slurry, sonicate for 10-30 min, vacuum dry the slurry to obtain a dry powder N, sift the dry powder N through a 400-600 mesh sieve, and embed the reinforcement only inside and obtaining a sieved material D which is a metal powder that has been filtered.

More preferably, the 400-600 mesh sieve in steps 1) and 2) is selected from stainless steel ultrasonic vibrating sieves, ultrasonic rotary vibrating sieves for ultrafine powder separation, and general vibrating sieves. Any kind.

More preferably, the vacuum drying temperature in the steps 1) and 2) is 60 to 80°C.

Preferably, said solvent is an aqueous solution, preferably ethanol.

Preferably, the frequency of ultrasound is preferably between 20 and 50 KHz.

Preferably, in the method for preparing a metallic material or metallic composite material of the present invention, the particulate phase B is iron, chromium, tungsten, silicon carbide, granular graphite, flake graphite, iron-chromium alloy, aluminum oxide, silicon carbide, It is a mixture of one or more of titanium carbide, hard ceramics, and tungsten carbide in an arbitrary ratio.

Preferably, in the method for preparing the metal material or metal composite material of the present invention, the mass ratio of the preliminary material and the phenol-formaldehyde resin powder is 20-99.5:0.5-2.

Preferably, in the method for preparing a metal material or metal composite material of the present invention, when the raw material contains the particle phase B, the mass ratio of the preliminary material, the phenol formaldehyde resin powder and the particle phase B is 20 to 99.5:0. 5-2: 0.5-78.

Preferably, in the method for preparing a metal material or a metal composite material of the present invention, the mixed material is cold-pressed to obtain a green compact, and then fired under pressure in a protective atmosphere or a vacuum or a protective atmosphere. to obtain a carbon/metal composite, or directly hot press the mixed powder to obtain a carbon/metal composite.

The press pressure in the cold press molding process is 200 to 600 MPa, the holding pressure time is 20 to 30 s, the temperature in the compact sintering process is 60% to 80% of the melting point of the matrix metal, and the heat retention time is 0. .5 to 3 hours, and the pressure is 0 to 1 MPa.

The unit pressure in the hot pressing process is 200-600 MPa, the temperature is 60%-80% of the melting point of the matrix metal, and the heat and pressure holding time is 2-90 min.

Preferably, in the method for preparing a metal material or metal composite material of the present invention, the density of the obtained carbon/metal composite material is 99% or more.

In a preferred method of the present invention, the carbon material is innovatively pre-ball milled to be embedded in the matrix metal, and then innovatively combined with ultrasonic treatment and low-temperature heating-quenching process to expose the carbon outside the metal. By removing the carbon in the embedded metal powder, the sintering diffusion in the matrix metal is effectively improved, and the sintering compactness is significantly improved. Finally, the phenol formaldehyde resin powder is added in the mixing process, Almost complete densification sintering is achieved by reducing atmosphere caused by high temperature decomposition during sintering of micron and submicron level phenol formaldehyde resin. According to the preparation method provided by the present invention, a metal matrix composite material having high strength, high toughness, high temperature resistance and excellent wear resistance is obtained after realizing sintering and densification of metal powder, Simple preparation process and low cost.

In the present invention, matrix metal A may be any matrix metal material for preparing carbon reinforced composites known to those skilled in the alloy arts.

Preferably, said matrix metal A oxide is non-reducible or poorly reducible in a reducing atmosphere of one or more of H ₂ , CO, said matrix metal A being for example aluminum, titanium, zirconium. at least one.

and/or the oxide of said matrix metal A is reducible in a reducing atmosphere of one or _more of H2, CO, said matrix metal A being e.g. copper, iron, nickel, chromium, manganese, silver is one of

Preferably, said matrix metal A is at least one of aluminum, titanium, zirconium, copper, iron, nickel, chromium, manganese and silver.

The method is particularly suitable for metal materials where carbon material on the surface of the carbon-embedded metal powder is difficult to remove by the surface pre-oxidation-reduction process.

More preferably, the matrix metal A is at least one of aluminum, titanium and zirconium.

Preferably, the carbon material and the matrix metal A are ball-milled to embed the carbon material in the matrix metal in advance. In this way, a metal powder with a uniform distribution of the carbon material can be obtained, which can improve the performance of the prepared composite material, and the innovative combination of ultrasonic treatment in the present invention allows the prepared composite material to performance can be further significantly improved.

Preferably, the volume ratio of the carbon material to the matrix metal A is 5-95:95-5 during the preparation of the carbon-embedded metal powder. By controlling this ratio, the performance of the prepared composite material can be further improved, and in particular, the mechanical properties and wear resistance can be significantly improved.

The present invention can effectively remove the carbon material remaining on the surface by innovatively using an ultrasonic method to remove the carbon material remaining on the surface of the carbon-embedded metal powder, and , is particularly suitable for surface decarburization of matrix metals for which preliminary oxidation-reduction treatment is difficult.

Using sieved material D or sieved material D and particulate phase B, the carbon-reinforced metal composite material is prepared by conventional mixing and conventional sintering processes.

The particulate phase B is any one or more of iron, chromium, tungsten, silicon carbide, granular graphite, flaky graphite, iron-chromium alloy, aluminum oxide, silicon carbide, titanium carbide, hard ceramics, and tungsten carbide. are mixed at a ratio of

The particle size of the particle phase B is preferably 10 to 400 μm.

As a preferred method, the mass ratio of the preliminary material and the phenol formaldehyde resin powder is 20-99.5:0.5-2.

As a preferred method, when the raw material contains the particle phase B, the mass ratio of the preliminary material, the phenol-formaldehyde resin powder and the particle phase B is 20-99.5:0.5-2:0.5-78.

Depending on the properties of the matrix metal, the mixed material may be sintered by existing methods to prepare the composite material.

Preferably, after cold-pressing the mixed material after mixing, a green compact is obtained, and then sintered under a protective atmosphere or under pressure in a vacuum or a protective atmosphere to obtain a carbon / metal composite material, or mixed The powder is hot-pressed directly to obtain a carbon/metal composite. The temperature of the cold press molding process is, for example, room temperature, preferably 15-35°C.

The press pressure in the cold press molding process is 200 to 600 MPa, the holding pressure time is 20 to 30 s, the temperature in the compact sintering process is 60% to 80% of the melting point of the matrix metal, and the heat retention time is 0. .5 to 3 hours, and the pressure was 0 to 1 MPa.

The unit pressure in the hot pressing process is 200-600 MPa, the temperature is 60%-80% of the melting point of the matrix metal, and the heat and pressure holding time is 2-90 min.

If the designed composite is a carbon/metal composite, a more preferred method of preparation involves the following steps.

process one

Ultrasonic treatment of carbon-embedded metal powders

The sonication process of the carbon-embedded metal powder (carbon-embedded metal powder) is as follows.

Metal powder with carbon embedded on the surface and inside (carbon-embedded metal powder) is added to alcohol to obtain a mixed solution, ultrasonically treated for 10 to 30 minutes, and the mixed solution is vacuum-dried to obtain dry powder M. Then, the dried powder M is passed through a 400-600 mesh sieve to obtain a sieved material C, which is a metal powder from which carbon has been removed from the primary surface.

Furthermore, after the obtained sieved material C was heat-treated under vacuum conditions at 150 to 300° C. for 30 to 60 minutes, it was placed in liquid nitrogen and heat-retained for 5 to 10 minutes, and the sieved material C after the treatment was added to alcohol. to obtain a slurry, sonicate for 10 to 30 minutes, vacuum dry the slurry, obtain a dry powder N, sieve the dry powder N through a 400 to 600 mesh, and obtain a metal powder in which carbon is embedded only inside A sieved material D is obtained.

Process 2

According to the design, the carbon-embedded metal powder after ultrasonic treatment obtained in step 1, the phenol-formaldehyde resin powder, and the component powder of the particle phase B are blended and uniformly mixed to obtain a mixed powder.

Process three

The mixed powder obtained in step 2 is cold-pressed to obtain a green compact, which is then sintered under any of protective atmosphere, vacuum, or pressure in a protective atmosphere to obtain a carbon/metal composite material. Alternatively, the mixed powder is directly hot-pressed to obtain a carbon/metal composite.

If the designed composite material is a carbon/metal composite material, in step 2, during mixing, it is stirred by a V-type mixer until uniform, and the stirring speed of the V-type mixer is 45-120 r/min; Mixing time is 2-8 h.

If the designed composite material is a carbon/metal composite material, in step 4, the pressing pressure of the cold press is 200-600 MPa, and the holding time is 20-30 s.

When the designed composite material is a carbon/metal composite material, the sintering temperature is 60% to 80% of the melting point of the matrix metal, the heat retention time is 0.5 to 3 hours, and the pressure is 0 to 1 MPa. there were.

When the designed composite material is a carbon/metal composite material, the hot pressing pressure is 200-600 MPa, the hot pressing temperature is 60%-80% of the melting point of the matrix metal, and the heat and pressure holding time is 2. ~90 min.

According to the preparation method of the metal material or metal composite material of the present invention, the compactness of the obtained metal material or metal composite material is above 99%, and can reach 99.8% after optimization.

The present invention uses reinforced metal powder (containing carbon) instead of metal powder as raw material, combines ultrasonic treatment and low temperature heating-quenching process, adds phenol formaldehyde resin powder during mixing, press- It was attempted for the first time that high-performance metallic materials or metallic composites (including carbon/metal composites) could be obtained by sintering.

The principles and advantages of the present invention are as follows.

Regarding the selection of raw materials, the use of carbon-enhanced metal powders instead of metal powders significantly improves the dispersion of carbon in the matrix. Types of carbon include artificial graphite, granular graphite, carbon fibers, carbon particles after crushing carbon fibers, and the like. In conventional mixing processes, carbon tends to agglomerate naturally, resulting in highly non-uniform distribution in the matrix, reducing the mechanical properties and wear resistance of the material. If a carbon-reinforced metal powder raw material can be formed in advance from carbon by a process such as ball milling and then added, the degree of dispersion of carbon in the matrix is significantly improved, and the overall performance is significantly improved.

Regarding the selection of the surface decarburization process, the sintering densification of powder is mainly carried out by atomic diffusion between particles, and the oxide film and heterogeneous phase on the surface of metal particles become interfaces that hinder sintering. , reducing the sintering densification between the powder particles. By using carbon particle reinforced metal powder instead of metal powder, uniform dispersion of carbon in the matrix can be achieved, but carbon exposed outside the metal powder also hinders sintering diffusion between metal particles. . Oxidation in an aerobic environment can remove surface carbon, but it also causes metal oxidation, e.g., aluminum oxide formed from aluminum powder is not reducible by hydrogen gas, nor is it reducible by CO, In the case of such metal powders, the surface decarburization and reduction process by oxidation cannot be used, so we chose to use a combination of ultrasonic treatment and low-temperature heating-quenching process, thus reducing the surface of the metal powder. of carbon can be removed, which aids subsequent press sintering of the powder.

Regarding the addition of phenol-formaldehyde resin powder during mixing, the inventor in Chinese invention patent CN108018506A describes that the surface functionalization is achieved by immersing materials such as graphite and carbon fiber in a saturated solution of phenol-formaldehyde resin and alcohol. It was proposed to modify the graphite surface and protect the carbon fiber structure with a resin coating layer formed after low-temperature curing, which can effectively remove the groups and has a very high wetting speed. However, the thickness of the coating layer after curing is several hundred microns, even several millimeters, and it decomposes at high temperature during sintering to generate gas, but the size of the carbon left by decomposition is coarse (submicron level). ), which increases the porosity of the material. For this reason, in this patent, phenol formaldehyde resin powder is used instead of a saturated solution of phenol formaldehyde resin, and micron or submicron level phenol formaldehyde resin powder is added during mixing, uniformly dispersed in the mixed material, and after pressing During high _- temperature sintering, the powder is uniformly decomposed in the material to release reducing gases such as H2, CO, etc., effectively reducing the oxide film on the metal surface, promoting the sintering of the metal, and , The carbon left by the decomposition of phenol-formaldehyde resin powder is porous and very thin activated carbon, which is easy to react with H2 to produce reducing _CH4 gas, at this time, the added phenol _- formaldehyde resin powder Most of it decomposes into gas, while the rest decomposes into a nanometer-level thick carbon film. When the carbon film is thin due to the diffusion of carbon and metal atoms, a rivet structure is formed in which the metal atoms penetrate the carbon film. , proposed to provide the necessary conditions for the realization of almost fully densified sintering of metals.

The preparation process is simple, low cost, and uses a combination of ultrasonication and low temperature heating-quenching processes to prepare composite materials based on carbon-reinforced metal powders by simply adding phenol-formaldehyde resin powder during mixing. Realize

The morphology of the carbon-enhanced metal powder is shown in FIG. A composite prepared from the carbon-reinforced metal powder as-is without any treatment is shown in FIG. A composite material prepared by subjecting the carbon-reinforced metal powder to sonication and drying is shown in FIG. As can be seen from FIG. 2, a large amount of carbon is exposed on the surface of the carbon-enhanced metal powder, impeding subsequent sintering. As can be seen from FIG. 3, the carbon-reinforced metal powder as raw material is mixed-pressed-sintered without any treatment, and the composite material has a large number of pores due to carbon interface failures. As can be seen from FIG. 4, by using a combination of ultrasonic treatment and low-temperature heating-quenching process, sintering and densification between metal particles is realized, and a metal matrix composite material with a density of 99% or more is obtained. The resulting composite material has good performance, uniformity and good market prospects.

1 is a preparation flow chart of a carbon/metal composite provided by the present invention;

SEM morphology of carbon-enhanced copper powder.

This is a composite material prepared using the carbon-reinforced copper powder as a raw material in Comparative Example 1 without any treatment.

It is a copper-based composite material prepared by subjecting the carbon-reinforced copper powder in Example 1 to ultrasonication-drying, mixing with phenol-formaldehyde resin powder, and finally pressing-sintering.

As can be seen from FIG. 1, the preparation flow of the carbon/metal composite designed according to the present invention is specifically as follows. First, the surface of the carbon-reinforced metal powder is subjected to ultrasonic treatment and low-temperature heating-quenching to remove carbon, then generally mixed with phenol-formaldehyde resin powder, hard particle phase, etc., and finally press-sintering treatment. to obtain a carbon/metal composite material.

As can be seen from FIGS. 2 and 3, a large amount of carbon is exposed on the surface of the carbon-reinforced metal powder, and if this is used as a raw material without any treatment, sintering and densification between the metal powder particles can be achieved. Can not.

As can be seen from FIG. 4, the combined use of ultrasonic treatment and low-temperature heating-quenching process achieves sintering densification between metal particles, and the addition of phenol-formaldehyde resin powder during mixing results in low porosity. is obtained.

The following clearly and completely describes the technical solution of the present invention with reference to the drawings of the present invention, but the described embodiments are only some embodiments of the technical solution described in the present invention. not all embodiments. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts shall all fall within the protection scope of the present invention.

Comparative example 1

In Comparative Example 1, the conditions were the same as in Example 1, except that the copper powder embedded with granular graphite prepared by ball milling was directly subjected to press-hydrogen pressure sintering at room temperature. The process was the same as in Example 1, except that the sonication and cold-quenching treatments were omitted. The prepared copper-based composite material had a high porosity of 14%, no diffusion sintering between metal particles, and a bending strength of 350 MPa.

Comparative example 2

In this Comparative Example 2, granular graphite was added to a ball mill together with electrolytic copper powder, and high-energy ball milling was performed. The volume ratio of copper powder and granular graphite is 5:1, the ball milling rotation speed is 280 r/min, the ball milling time is 8 hours, the balls for ball milling are stainless steel balls, and the ball diameter is 3 mm. 10 mm (the mass ratio was 4:8:11:20:12:8:6:1 when the ball milling balls had diameters of 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, and 9 mm) ), and the mass ratio of the sum of the masses of the granular graphite and the electrolytic copper powder to the balls for ball milling was 1:6.

After the ball milling, the copper powder embedded with granular graphite and alcohol were mixed, ultrasonicated for 120 minutes (the ultrasonic frequency was 35 KHz), the temperature of the solution was maintained at room temperature, and the mixture was further ultrasonicated. After the treated solution is vacuum dried at 60° C., it is sieved with an ultrasonic rotary vibrating sieve, and the minimum mesh size of the screen is 400 mesh. left. Further, after the powder is vacuum-retained at 150°C for 30 minutes, it is directly placed in liquid nitrogen and kept warm for 10 minutes, then mixed with alcohol, ultrasonicated for 20 minutes, and finally the solution after ultrasonication is vacuum-dried at 60°C. After that, the powder was sieved by an ultrasonic rotary vibrating sieve for ultrafine powder separation to obtain a copper powder in which granular graphite was embedded only inside.

The copper powder with granular graphite embedded only inside is directly cold-pressed at room temperature, the press pressure is 450 MPa, the pressure holding time is 20 s, and the prepared copper-based composite material compact is protected under a hydrogen atmosphere. and sintered at 960 ° C. for 2 hours, the pressure is 0.85 MPa, and the temperature increase rate and temperature decrease rate of the furnace are both 10 to 15 ° C./min, and a sample of Comparative Example 2 is obtained. rice field. The denseness of the copper-based composite material was 98%, and the bending strength was 450 MPa.

Comparative example 3

In this Comparative Example 3, granular graphite was added to a ball mill together with electrolytic copper powder, and high-energy ball milling was performed. The volume ratio of copper powder and granular graphite is 5:1, the ball milling rotation speed is 280 r/min, the ball milling time is 8 hours, the balls for ball milling are stainless steel balls, and the ball diameter is 3 mm. 10 mm (the mass ratio was 4:8:11:20:12:8:6:1 when the ball milling balls had diameters of 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, and 9 mm) ), and the mass ratio of the sum of the masses of the granular graphite and the electrolytic copper powder to the balls for ball milling was 1:6.

After the ball milling, the copper powder embedded with granular graphite and alcohol were mixed, ultrasonicated for 120 minutes (the ultrasonic frequency was 35 KHz), the temperature of the solution was maintained at room temperature, and the mixture was further ultrasonicated. After the treated solution is vacuum dried at 60° C., it is sieved with an ultrasonic rotary vibrating sieve, and the minimum mesh size of the screen is 400 mesh. left. Further, after the powder is vacuum-retained at 150°C for 30 minutes, it is directly placed in liquid nitrogen and kept warm for 10 minutes, then mixed with alcohol, ultrasonicated for 20 minutes, and finally the solution after ultrasonication is vacuum-dried at 60°C. After that, the powder was sieved by an ultrasonic rotary vibrating sieve for ultrafine powder separation to obtain a copper powder in which granular graphite was embedded only inside.

Copper powder with granular graphite embedded only inside is immersed in an alcohol saturated solution of phenol formaldehyde resin for 2 hours, dried at 100 ° C. for 2 hours, crushed and directly cold-pressed at room temperature, press pressure is 450 MPa, The pressure holding time is 20 s, the prepared copper-based composite material compact is pressure sintered under the protection of a hydrogen atmosphere, sintered at 960 ° C. for 2 h, the pressure is 0.85 MPa, and the furnace is raised. Both the heating rate and the cooling rate were 10 to 15° C./min, and a sample of Comparative Example 3 was obtained. The denseness of the copper-based composite material was 96%, and the bending strength was 375 MPa.

Comparative example 4

In Comparative Example 4, the other conditions were the same as in Example 1, except that the particle size of the phenol formaldehyde resin powder added during mixing was 1 to 2 mm. The process was the same as in Example 1, except that the sonication and cold-quenching treatments were omitted. The prepared copper-based composite material had a high porosity of 15%, no diffusion sintering between metal particles, and a bending strength of 333 MPa.

Example 1

In Example 1, granular graphite was added to a ball mill together with electrolytic copper powder, and high-energy ball milling was performed. The volume ratio of copper powder and granular graphite is 5:1, the ball milling rotation speed is 280 r/min, the ball milling time is 8 hours, the balls for ball milling are stainless steel balls, and the ball diameter is 3 mm. 10 mm (the mass ratio was 4:8:11:20:12:8:6:1 when the ball milling balls had diameters of 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, and 9 mm) ), and the mass ratio of the sum of the masses of the granular graphite and the electrolytic copper powder to the balls for ball milling was 1:6.

After the ball milling, the copper powder embedded with granular graphite and alcohol were mixed, ultrasonicated for 120 minutes (the ultrasonic frequency was 35 KHz), the temperature of the solution was maintained at room temperature, and the mixture was further ultrasonicated. After the treated solution is vacuum dried at 60° C., it is sieved with an ultrasonic rotary vibrating sieve, and the minimum mesh size of the screen is 400 mesh. left. Further, after the powder is vacuum-retained at 150°C for 30 minutes, it is directly placed in liquid nitrogen and kept warm for 10 minutes, then mixed with alcohol, ultrasonicated for 20 minutes, and finally the solution after ultrasonication is vacuum-dried at 60°C. After that, the powder was sieved by an ultrasonic rotary vibrating sieve for ultrafine powder separation to obtain a copper powder in which granular graphite was embedded only inside.

Copper powder in which granular graphite was embedded only inside and phenol formaldehyde resin powder with a particle size of 100 μm were mixed in a V-type mixer at a mass ratio of 99:1 to obtain a mixed powder. Furthermore, the mixed powder is cold-pressed at room temperature, the press pressure is 450 MPa, the pressure holding time is 20 s, and the prepared copper-based composite material green compact is pressure-sintered under the protection of a hydrogen atmosphere, and 960 ° C. The sample of Example 1 was obtained by sintering for 2 hours at a furnace temperature rise rate and temperature fall rate of 10 to 15° C./min and a pressure of 0.85 MPa. The morphology of the prepared copper-based composite is shown in FIG. The denseness of the copper-based composite material was 99.5%, and the bending strength was 500 MPa.

Comparative example 5

In Comparative Example 5, the conditions were the same as in Example 2, except that the carbon particle-embedded copper powder prepared by ball milling was directly subjected to press-hydrogen sintering at room temperature. , was the same as Example 2, except that the sonication and cold-quenching treatments were not performed. The morphology of the prepared copper-based composite is shown in FIG. The porosity was as high as 10%, diffusion sintering did not occur between metal particles, and the bending strength was 380 MPa.

Comparative example 6

In Comparative Example 6, commercially available short carbon fibers were used, and the short carbon fibers had a diameter of 7 μm and a length of 1 mm. Under vacuum conditions, heat is kept at 700 ° C. for 60 minutes to degumming, and then added to a ball mill together with electrolytic copper powder to perform high-energy ball milling. , the volume ratio of the electrolytic copper powder and the degummed short carbon fiber is 3:1, the ball milling rotation speed is 250 r/min, the ball milling time is 6 h, and the balls for ball milling are stainless steel balls. , the ball diameter is 3 mm to 10 mm (when the ball milling ball diameter is 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, the mass ratio is 4: 8: 11: 20: 12: 8: 6 : 1), and the mass ratio of the sum of the degummed short fibers and the electrolytic copper powder to the balls for ball milling was 1:6. The SEM morphology of the prepared carbon particle-embedded copper powder is shown in FIG.

After ball milling, the copper powder embedded with ultrafine carbon powder and alcohol were mixed, ultrasonic treatment was applied for 120 min (the ultrasonic frequency was 25 KHz), the temperature of the solution was maintained at room temperature, and further After the ultrasonically treated solution was vacuum-dried at 60° C., it was sieved with an ultrasonic rotary vibrating sieve. It left behind metal powder. Further, after the powder is vacuum-retained at 150°C for 30 minutes, it is directly placed in liquid nitrogen and kept warm for 10 minutes, then mixed with alcohol, ultrasonicated for 20 minutes, and finally the solution after ultrasonication is vacuum-dried at 60°C. After that, the powder was sieved by an ultrasonic rotary vibrating sieve for ultrafine powder separation to obtain a copper powder in which ultrafine carbon was embedded only inside.

The copper powder with ultrafine carbon embedded only inside is directly cold-pressed at room temperature, the pressing pressure is 450 MPa, the pressure holding time is 20 s, and the prepared copper-based composite material compact is protected in a hydrogen atmosphere. The sample of Comparative Example 6 was sintered under pressure and sintered at 950° C. for 2 hours. Obtained. The denseness of the copper-based composite material was 99%, and the bending strength was 480 MPa.

Example 2

In Example 2, commercially available short carbon fibers were used, and the short carbon fibers had a diameter of 7 μm and a length of 1 mm. Under vacuum conditions, heat is kept at 700 ° C. for 60 minutes to degumming, then added to a ball mill together with electrolytic copper powder, high energy ball milling is performed, and the particle diameter of the electrolytic copper powder added is 150 μm. , the volume ratio of the electrolytic copper powder and the degummed short carbon fiber is 3:1, the ball milling rotation speed is 250 r/min, the ball milling time is 6 h, and the balls for ball milling are stainless steel balls. , the ball diameter is 3 mm to 10 mm (when the ball milling ball diameter is 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, the mass ratio is 4: 8: 11: 20: 12: 8: 6 : 1), and the mass ratio of the sum of the degummed short fibers and the electrolytic copper powder to the balls for ball milling was 1:6. The SEM morphology of the prepared carbon particle-embedded copper powder is shown in FIG.

After ball milling, the copper powder embedded with ultrafine carbon powder and alcohol were mixed, ultrasonic treatment was applied for 120 min (the ultrasonic frequency was 25 KHz), the temperature of the solution was maintained at room temperature, and further After the ultrasonically treated solution was vacuum-dried at 60° C., it was sieved with an ultrasonic rotary vibrating sieve. It left behind metal powder. Further, after the powder is vacuum-retained at 150°C for 30 minutes, it is directly placed in liquid nitrogen and kept warm for 10 minutes, then mixed with alcohol, ultrasonicated for 20 minutes, and finally the solution after ultrasonication is vacuum-dried at 60°C. After that, the powder was sieved by an ultrasonic rotary vibrating sieve for ultrafine powder separation to obtain a copper powder in which ultrafine carbon was embedded only inside.

A copper powder in which ultrafine carbon was embedded only inside and a phenol formaldehyde resin powder having a particle size of 200 μm were mixed at a mass ratio of 99:1 in a V-type mixer to obtain a mixed powder. Furthermore, the mixed powder is cold-pressed at room temperature, the press pressure is 450 MPa, the pressure holding time is 20 s, and the prepared copper-based composite material green compact is pressure-sintered under the protection of a hydrogen atmosphere, and 950 ° C. The sample of Example 2 was obtained by sintering for 2 hours at a pressure of 0.9 MPa and heating and cooling rates of the furnace both at 10 to 15° C./min. The denseness of the copper-based composite material was 99.8%, and the bending strength was 510 MPa.

Comparative example 7

In this Comparative Example 7, the other conditions were the same as in Example 3, except that the carbon fiber-embedded nickel powder prepared by ball milling was directly subjected to press-hydrogen sintering at room temperature. , was the same as Example 3, except that the sonication and cold-quenching treatments were not performed. The prepared nickel-based composite material had a high porosity of 10% and a tensile strength of 750 MPa.

Comparative example 8

In Comparative Example 8, commercially available short carbon fibers were used, and the short carbon fibers had a diameter of 8 μm and a length of 2 mm. After dissolving the blended phenol formaldehyde resin in an organic solvent to obtain an alcohol saturated solution of phenol formaldehyde resin, short carbon fibers were immersed in the alcohol saturated solution of phenol formaldehyde resin at 80° C. for 2 hours and then dried at 120° C. for 2 hours. did. Subsequently, it is added to a ball mill together with the electrolytic nickel powder, and subjected to high-energy ball milling. Yes, the ball milling rotation speed is 300 r/min, the ball milling time is 3 h, the ball milling ball is a stainless steel ball, and the ball diameter is 3 mm to 10 mm (the diameter of the ball milling ball is 3 mm, The mass ratio was 4: 8: 11: 20: 12: 8: 6: 1 when 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm), short fibers coated with phenol formaldehyde resin and electrolytic nickel The mass ratio of the sum of the mass of the powder and the balls for ball milling was 1:6.

After ball milling, the prepared nickel powder with short carbon fibers embedded inside and on the surface was mixed with alcohol, and ultrasonic treatment was added for 100 minutes (the ultrasonic frequency was 30 KHz). is maintained at room temperature, and the solution after ultrasonic treatment is vacuum-dried at 60 ° C., then sieved with an ultrasonic rotary vibrating sieve, the minimum mesh size of the screen is 400 mesh, and the sieved product, that is, the primary A metal powder with surface carbon removed was left behind. Further, after the powder is vacuum-retained at 180°C for 30 minutes, it is directly placed in liquid nitrogen and kept warm for 10 minutes, then mixed with alcohol, ultrasonicated for 20 minutes, and finally the solution after ultrasonication is vacuum-dried at 60°C. After that, it was sieved by an ultrasonic rotary vibrating sieve for ultrafine powder separation to obtain a nickel powder in which carbon fibers were embedded only inside.

The nickel powder with carbon fibers embedded only inside is directly cold-pressed at room temperature, the pressing pressure is 500 MPa, the pressure holding time is 20 s, and the prepared nickel-based composite material compact is protected under hydrogen atmosphere. and sintered at 1000 ° C. for 2 hours, the pressure is 0.8 MPa, and the temperature increase rate and temperature decrease rate of the furnace are both 10 to 15 ° C./min, and a sample of Comparative Example 8 is obtained. rice field. The nickel-based composite material had a density of 98.5% and a tensile strength of 1250 MPa.

Comparative example 9

In Comparative Example 9, commercially available short carbon fibers were used, and the short carbon fibers had a diameter of 8 μm and a length of 2 mm. After dissolving the blended phenol formaldehyde resin in an organic solvent to obtain an alcohol saturated solution of phenol formaldehyde resin, short carbon fibers were immersed in the alcohol saturated solution of phenol formaldehyde resin at 80° C. for 2 hours and then dried at 120° C. for 2 hours. did. Subsequently, it is added to a ball mill together with the electrolytic nickel powder, and subjected to high-energy ball milling. Yes, the ball milling rotation speed is 300 r/min, the ball milling time is 3 h, the ball milling ball is a stainless steel ball, and the ball diameter is 3 mm to 10 mm (the diameter of the ball milling ball is 3 mm, The mass ratio was 4: 8: 11: 20: 12: 8: 6: 1 when 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm), short fibers coated with phenol formaldehyde resin and electrolytic nickel The mass ratio of the sum of the mass of the powder and the balls for ball milling was 1:6.

After ball milling, the prepared nickel powder with short carbon fibers embedded inside and on the surface was mixed with alcohol, and ultrasonic treatment was added for 100 minutes (the ultrasonic frequency was 30 KHz). is maintained at room temperature, and the solution after ultrasonic treatment is vacuum-dried at 60 ° C., then sieved with an ultrasonic rotary vibrating sieve, the minimum mesh size of the screen is 400 mesh, and the sieved product, that is, the primary A metal powder with surface carbon removed was left behind. Further, after the powder is vacuum-retained at 180°C for 30 minutes, it is directly placed in liquid nitrogen and kept warm for 10 minutes, then mixed with alcohol, ultrasonicated for 20 minutes, and finally the solution after ultrasonication is vacuum-dried at 60°C. After that, it was sieved by an ultrasonic rotary vibrating sieve for ultrafine powder separation to obtain a nickel powder in which carbon fibers were embedded only inside.

Nickel powder with carbon fibers embedded only inside was immersed in an alcohol saturated solution of phenol formaldehyde resin for 2 hours, dried at 100 ° C. for 2 hours, crushed, and directly cold-pressed at room temperature. Pressure time is 20 s, the prepared nickel-based composite material compact is pressure sintered under the protection of hydrogen atmosphere, sintered at 1000 ° C. for 2 h, pressure is 0.8 MPa, furnace temperature rise Both the rate and temperature drop rate were 10 to 15° C./min, and a sample of Comparative Example 9 was obtained. The nickel-based composite material had a density of 96.8% and a tensile strength of 1140 MPa.

Example 3

In Example 3, commercially available short carbon fibers were used, and the short carbon fibers had a diameter of 8 μm and a length of 2 mm. After dissolving the blended phenol formaldehyde resin in an organic solvent to obtain an alcohol saturated solution of phenol formaldehyde resin, short carbon fibers were immersed in the alcohol saturated solution of phenol formaldehyde resin at 80° C. for 2 hours and then dried at 120° C. for 2 hours. did. Subsequently, it is added to a ball mill together with the electrolytic nickel powder, and subjected to high-energy ball milling. Yes, the ball milling rotation speed is 300 r/min, the ball milling time is 3 h, the ball milling ball is a stainless steel ball, and the ball diameter is 3 mm to 10 mm (the diameter of the ball milling ball is 3 mm, The mass ratio was 4: 8: 11: 20: 12: 8: 6: 1 when 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm), short fibers coated with phenol formaldehyde resin and electrolytic nickel The mass ratio of the sum of the mass of the powder and the balls for ball milling was 1:6.

After ball milling, the prepared nickel powder with short carbon fibers embedded inside and on the surface was mixed with alcohol, and ultrasonic treatment was added for 100 minutes (the ultrasonic frequency was 30 KHz). is maintained at room temperature, and the solution after ultrasonic treatment is vacuum-dried at 60 ° C., then sieved with an ultrasonic rotary vibrating sieve, the minimum mesh size of the screen is 400 mesh, and the sieved product, that is, the primary A metal powder with surface carbon removed was left behind. Further, after the powder is vacuum-retained at 180°C for 30 minutes, it is directly placed in liquid nitrogen and kept warm for 10 minutes, then mixed with alcohol, ultrasonicated for 20 minutes, and finally the solution after ultrasonication is vacuum-dried at 60°C. After that, it was sieved by an ultrasonic rotary vibrating sieve for ultrafine powder separation to obtain a nickel powder in which carbon fibers were embedded only inside.

Nickel powder in which carbon fibers were embedded only inside and phenol formaldehyde resin powder with a particle size of 200 μm were mixed at a mass ratio of 99:1 in a V-type mixer to obtain a mixed powder. Further, the mixed powder is cold-pressed at room temperature, the press pressure is 500 MPa, the pressure holding time is 20 s, and the prepared nickel-based composite material compact is pressure-sintered under the protection of a hydrogen atmosphere, and is heated to 1000 ° C. The sample of Example 3 was obtained by sintering for 2 hours at a pressure of 0.8 MPa, and heating and cooling rates of the furnace were both 10 to 15° C./min. The nickel-based composite material had a density of 99.2% and a tensile strength of 1310 MPa.

Comparative example 10

In Comparative Example 10, aluminum powder with carbon fibers embedded therein prepared by ball milling and 2% silicon carbide were blended and then mixed in a V-type mixer to obtain a mixed powder. The conditions were the same as in Example 4. The obtained mixed powder was hot-pressed at 490° C. under the protection of a nitrogen atmosphere with a press pressure of 500 MPa and a hot-press time of 0.5 h to obtain an aluminum matrix composite material. The compactness was only 92% and the bending strength was 700 MPa.

Comparative example 11

The aluminum matrix composite material prepared in this Comparative Example 11 contained 2% by mass of silicon carbide and the balance of aluminum alloy powder in which short carbon fibers were embedded. The particle size of the silicon carbide was 90 µm, and the particle size of the aluminum alloy powder in which short carbon fibers were embedded was 100 µm. The short carbon fibers had a diameter of 8 μm and a length of 2 mm.

After dissolving the blended phenol formaldehyde resin in an organic solvent to obtain an alcohol saturated solution of phenol formaldehyde resin, short carbon fibers were immersed in the alcohol saturated solution of phenol formaldehyde resin at 80° C. for 2 hours and then dried at 120° C. for 2 hours. did. The hardened phenol formaldehyde resin carbon fiber and Al-9.6 wt% Zn-2.5 wt% Mg-2.2 wt% Cu-0.16 wt% Zr atomized alloy powder with a particle size of 150 μm are ball-milled, and the carbon fiber is The volume percentage is 8%, the aluminum alloy powder is added so that the volume percentage is 92%, the ball milling rotation speed is 300 r/min, the ball milling time is 2 hours, and the mass ratio of the ball to the material is was 6:1, the ball milling balls were stainless steel balls and cemented carbide balls, and the ball diameter was 3 mm to 10 mm (the diameter of the ball milling ball was 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, The mass ratio for 8 mm and 9 mm was 4:8:11:20:12:8:6:1).

After ball milling, the prepared aluminum powder with carbon fibers embedded inside and on the surface was mixed with alcohol, and ultrasonic treatment was added for 120 minutes (the ultrasonic frequency was 28 KHz), and the temperature of the solution was increased to After the solution was kept at room temperature and vacuum-dried at 60° C., the solution was sieved with an ultrasonic rotary vibrating sieve to leave the sieved material, that is, the metal powder from which carbon on the primary surface was removed. Further, after the powder is vacuum-retained at 200°C for 30 minutes, it is directly placed in liquid nitrogen and kept warm for 10 minutes, then mixed with alcohol, ultrasonicated for 20 minutes, and finally the solution after ultrasonication is vacuum-dried at 60°C. After that, it was sieved by an ultrasonic rotary vibrating sieve for ultrafine powder separation to obtain an aluminum powder in which carbon fibers were embedded only inside.

An aluminum alloy powder with a particle diameter of 180 μm and carbon fibers remaining only inside, and an aluminum alloy powder with carbon fibers remaining only inside in terms of mass percentage of 98.0% and silicon carbide so that the powder is 2%. were blended and mixed in a V-type mixer to obtain a mixed powder. The obtained mixed powder was hot-pressed at 490° C. under the protection of a nitrogen atmosphere with a press pressure of 500 MPa and a hot-press time of 0.5 h to obtain an aluminum matrix composite material. The denseness was 99% and the bending strength was 860 MPa.

Example 4

The aluminum matrix composite material prepared in this Example 4 contained 2% by mass of silicon carbide and the balance of short carbon fiber-embedded aluminum alloy powder. The particle size of the silicon carbide was 90 µm, and the particle size of the aluminum alloy powder in which short carbon fibers were embedded was 100 µm. The short carbon fibers had a diameter of 8 μm and a length of 2 mm.

After dissolving the blended phenol formaldehyde resin in an organic solvent to obtain an alcohol saturated solution of phenol formaldehyde resin, short carbon fibers were immersed in the alcohol saturated solution of phenol formaldehyde resin at 80° C. for 2 hours and then dried at 120° C. for 2 hours. did. Ball milling of hardened phenol formaldehyde resin carbon fiber and Al-9.6 wt% Zn-2.5 wt% Mg-2.2 wt% Cu-0.16 wt% Zr atomized alloy powder with a particle size of 150 microns, carbon fiber is 8% by volume, aluminum alloy powder is added to be 92% by volume, the ball milling rotation speed is 300 r / min, the ball milling time is 10 h, and the mass of the ball and the material The ratio was 6:1, the ball milling balls were stainless steel balls and cemented carbide balls, and the ball diameter was 3 mm to 10 mm (ball milling ball diameters of 3 mm, 4 mm, 5 mm, 6 mm, 7 mm , 8 mm and 9 mm, the mass ratio was 4:8:11:20:12:8:6:1).

After ball milling, the prepared aluminum powder with carbon fibers embedded inside and on the surface was mixed with alcohol, and ultrasonic treatment was added for 120 minutes (the ultrasonic frequency was 28 KHz), and the temperature of the solution was increased to After the solution was kept at room temperature and vacuum-dried at 60° C., the solution was sieved with an ultrasonic rotary vibrating sieve to leave the sieved material, that is, the metal powder from which carbon on the primary surface was removed. Further, after the powder is vacuum-retained at 200°C for 30 minutes, it is directly placed in liquid nitrogen and kept warm for 2 minutes, then mixed with alcohol, ultrasonicated for 20 minutes, and finally the solution after ultrasonication is vacuum-dried at 60°C. After that, it was sieved by an ultrasonic rotary vibrating sieve for ultrafine powder separation to obtain an aluminum powder in which carbon fibers were embedded only inside.

Aluminum alloy powder (particle size is 180 μm) in which carbon fibers are embedded only inside, phenol formaldehyde resin powder (particle size is 250 μm), and silicon carbide are blended at a mass ratio of 96.5:1.5:2, A mixed material was obtained by mixing with a V-type mixer. The mixed material was hot-pressed at 490° C. under the protection of nitrogen atmosphere, the pressing pressure was 500 MPa, and the hot-pressing time was 0.5 h to obtain an aluminum matrix composite. The denseness was 99.5% and the bending strength was 882 MPa.

Comparative example 12

In Comparative Example 12, the conditions were the same as in Example 5, except that the ultrafine carbon-embedded iron powder prepared by ball milling was directly subjected to press-vacuum pressure sintering at room temperature. The process was the same as in Example 5, except that the sonication and cold-quenching treatments were omitted. The prepared iron-based composite material had a high porosity of 12% and a tensile strength of 610 MPa.

Comparative example 13

In Comparative Example 13, commercially available short carbon fibers degummed at 700° C. for 60 minutes and reduced iron powder with a particle size of 120 microns were used as raw materials for ball milling. Iron powder is added so that the volume percentage is 92%, the diameter of carbon short fibers is 6 μm and the length is 2 mm, both are added to a ball mill, high energy ball milling is performed, and the rotation speed is 250 r / min, the ball milling time is 6 h, the mass ratio of the ball to the material is 6: 1, the ball milling ball is a stainless steel ball and a cemented carbide ball, and the ball diameter is 3 mm to 10 mm. (The mass ratio was 4:8:11:20:12:8:6:1 when the ball milling balls had diameters of 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm and 9 mm).

After ball milling, the prepared iron powder with ultrafine carbon embedded inside and on the surface was mixed with alcohol, and ultrasonic treatment was added for 120 minutes (the ultrasonic frequency was 28 KHz), and the temperature of the solution was was maintained at room temperature, and the solution after ultrasonic treatment was vacuum-dried at 60 ° C. and then sieved with an ultrasonic rotary vibrating sieve to leave the sieved material, that is, the metal powder from which carbon on the primary surface was removed. . Further, after the powder is vacuum-retained at 200°C for 30 minutes, it is directly placed in liquid nitrogen and kept warm for 10 minutes, then mixed with alcohol, ultrasonicated for 20 minutes, and finally the solution after ultrasonication is vacuum-dried at 60°C. After that, the powder was sieved by an ultrasonic rotary vibrating sieve for ultrafine powder separation to obtain an iron powder in which ultrafine carbon was embedded only inside.

The iron powder with ultrafine carbon embedded only inside is directly cold-pressed at room temperature, the press pressure is 550 MPa, the holding pressure time is 20 s, and the prepared iron alloy compact is pressed under vacuum protection. After sintering at 1050° C. for 2 hours, the pressure was 0.3 MPa, and the heating rate and cooling rate of the furnace were both 10 to 15° C./min to obtain an iron-based composite material. The compactness was 98.5% and the tensile strength was 750 MPa.

Example 5

In Example 5, commercially available short carbon fibers degummed at 700 ° C. for 60 minutes and reduced iron powder with a particle size of 120 microns were used as raw materials for ball milling. Iron powder is added so that the volume percentage is 92%, the diameter of carbon short fibers is 6 μm and the length is 2 mm, both are added to a ball mill, high energy ball milling is performed, and the rotation speed is 250 r / min, the ball milling time is 6 h, the mass ratio of the ball to the material is 6: 1, the ball milling ball is a stainless steel ball and a cemented carbide ball, and the ball diameter is 3 mm to 10 mm. (The mass ratio was 4:8:11:20:12:8:6:1 when the ball milling balls had diameters of 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm and 9 mm).

After ball milling, the prepared iron powder with ultrafine carbon embedded inside and on the surface was mixed with alcohol, and ultrasonic treatment was added for 120 minutes (the ultrasonic frequency was 28 KHz), and the temperature of the solution was was maintained at room temperature, and the solution after ultrasonic treatment was vacuum-dried at 60 ° C. and then sieved with an ultrasonic rotary vibrating sieve to leave the sieved material, that is, the metal powder from which carbon on the primary surface was removed. . Further, after the powder is vacuum-retained at 200°C for 30 minutes, it is directly placed in liquid nitrogen and kept warm for 10 minutes, then mixed with alcohol, ultrasonicated for 20 minutes, and finally the solution after ultrasonication is vacuum-dried at 60°C. After that, the powder was sieved by an ultrasonic rotary vibrating sieve for ultrafine powder separation to obtain an iron powder in which ultrafine carbon was embedded only inside.

Iron powder in which ultrafine carbon was embedded only inside and phenol formaldehyde resin powder with a particle size of 150 μm were blended at a mass ratio of 98:2 and mixed in a V-type mixer to obtain a mixed powder. The obtained mixed powder is cold-pressed at room temperature, the press pressure is 550 MPa, the pressure holding time is 20 s, and the prepared iron alloy compact is pressure-sintered under vacuum protection, and is heated to 1050 ° C. for 2 h. After sintering, the pressure was 0.3 MPa, and the heating rate and cooling rate of the furnace were both 10 to 15° C./min to obtain an iron-based composite material. The compactness was 99.5% and the tensile strength was 860 MPa.

Comparative example 14

In Comparative Example 14, the conditions were the same as in Example 6, except that the ultrafine carbon-embedded titanium powder prepared by ball milling was directly subjected to press-vacuum sintering at room temperature. was the same as Example 6, except that the ultrasonic treatment and the cold-quenching treatment were not performed. The prepared titanium-based composite material had a high porosity of 11% and a tensile strength of 950 MPa.

Comparative example 15

In this Comparative Example 15, commercially available carbon short fibers degummed at 800 ° C. for 30 minutes and titanium alloy powder with a particle size of 50 microns (Ti-6 wt% Al-2.8 wt% Sn-3.5 wt% Zr- 0.75 wt% Nb-0.35 wt% Si) was used as a ball milling raw material (the volume ratio of titanium alloy powder to short carbon fibers after degumming was 5:1). The short carbon fiber has a diameter of 6 μm and a length of 2 mm. Both are added to a ball mill and subjected to high energy ball milling. The ball for ball milling is a cemented carbide ball, and the ball diameter is 3 mm to 9 mm (when the diameter of the ball milling ball is 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, and 9 mm, the mass ratio is 4:8: 11:20:12:8:6:1), and the mass ratio of the sum of the degummed short fibers and the titanium alloy powder to the balls for ball milling was 1:8.

After the ball milling, the prepared titanium alloy powder having ultrafine carbon embedded inside and on the surface was mixed with alcohol, and ultrasonic treatment was applied for 120 minutes (the ultrasonic frequency was 28 KHz) to obtain a solution. The temperature is maintained at room temperature, and the ultrasonically treated solution is vacuum dried at 60° C. and then sieved with an ultrasonic rotary vibrating sieve to leave the sieved material, that is, the metal powder from which carbon on the primary surface has been removed. rice field. Further, after the powder is vacuum-retained at 400°C for 30 minutes, it is directly placed in liquid nitrogen and kept warm for 10 minutes, then mixed with alcohol, ultrasonicated for 20 minutes, and finally the solution after ultrasonication is vacuum-dried at 60°C. After that, it was sieved by an ultrasonic rotary vibrating sieve for ultrafine powder separation to obtain a titanium alloy powder in which ultrafine carbon was embedded only inside.

The titanium alloy powder with ultrafine carbon remaining only inside is cold-pressed at room temperature, the press pressure is 400 MPa, the pressure holding time is 20 s, and the prepared titanium-based composite material compact is baked under vacuum. After sintering at 1350° C. for 2 hours, both the heating rate and cooling rate of the furnace were 15° C./min to obtain a titanium-based composite material. The compactness was 98% and the tensile strength was 1240 MPa.

Example 6

In Example 6, commercially available carbon short fibers degummed at 800 ° C. for 30 minutes and titanium alloy powder with a particle size of 50 μm (Ti-6 wt% Al-2.8 wt% Sn-3.5 wt% Zr-0 .75 wt% Nb-0.35 wt% Si) was used as a ball milling raw material (the volume ratio of titanium alloy powder to short carbon fibers after degumming was 5:1). The short carbon fiber has a diameter of 6 μm and a length of 2 mm. Both are added to a ball mill and subjected to high energy ball milling. The ball for ball milling is a cemented carbide ball, and the ball diameter is 3 mm to 9 mm (when the diameter of the ball milling ball is 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, and 9 mm, the mass ratio is 4:8: 11:20:12:8:6:1), and the mass ratio of the sum of the degummed short fibers and the titanium alloy powder to the balls for ball milling was 1:8.

After the ball milling, the prepared titanium alloy powder having ultrafine carbon embedded inside and on the surface was mixed with alcohol, and ultrasonic treatment was applied for 120 minutes (the ultrasonic frequency was 28 KHz) to obtain a solution. The temperature is maintained at room temperature, and the ultrasonically treated solution is vacuum dried at 60° C. and then sieved with an ultrasonic rotary vibrating sieve to leave the sieved material, that is, the metal powder from which carbon on the primary surface has been removed. rice field. Further, after the powder is vacuum-retained at 400°C for 30 minutes, it is directly placed in liquid nitrogen and kept warm for 10 minutes, then mixed with alcohol, ultrasonicated for 20 minutes, and finally the solution after ultrasonication is vacuum-dried at 60°C. After that, it was sieved by an ultrasonic rotary vibrating sieve for ultrafine powder separation to obtain a titanium alloy powder in which ultrafine carbon was embedded only inside.

A titanium alloy in which ultrafine carbon was embedded only inside and phenol formaldehyde resin powder with a particle size of 150 μm were blended at a mass ratio of 98:2 and mixed in a V-type mixer to obtain a mixed powder. The obtained mixed powder was cold-pressed at room temperature, the press pressure was 400 MPa, the holding time was 20 s, and the prepared titanium-based composite material green compact was sintered under vacuum and baked at 1350 ° C. for 2 h. As a result, both the temperature rise rate and the temperature drop rate of the furnace were 15° C./min, and a titanium-based composite material was obtained. The compactness was 98.8% and the tensile strength was 1365 MPa.

Example 7

In Example 7, the preparation process, mixing, and pressing process of the iron powder in which ultrafine carbon was embedded only inside were the same as in Example 5, except that the sintering process was different. In the sintering process, the green compact is pressure-sintered under vacuum protection, sintered at 750° C. for 2 hours, further heated to 1100° C. and sintered for 2 hours. was 10 to 15° C./min and the pressure was 0.5 MPa to obtain an iron alloy reinforced with ultrafine iron carbide particles. The compactness was 99.2% and the tensile strength was 865 MPa.

Claims (10)

strengthThe metal powder with the reinforcing body embedded in the surface and inside is obtained by ball milling the hardened body and the matrix metal A, and the metal powder with the reinforcing body embedded is subjected to ultrasonic treatment and low-temperature heating-quenching process to obtain the surface. After removing the reinforcing particles to obtain a preliminary material, mixing the preliminary material and the phenol formaldehyde resin powder, press-sintering is performed, or after mixing the preliminary material, the phenol formaldehyde resin powder and the particle phase B, press- sintered to obtain a carbon/metal composite,
The reinforcing body is at least one selected from carbon materials and carbides,
The matrix metal A is at least one of aluminum, titanium, zirconium, copper, iron, nickel, chromium, manganese and silver,
The particulate phase B is any one or more of iron, chromium, tungsten, silicon carbide, granular graphite, flake graphite, iron-chromium alloy, aluminum oxide, silicon carbide, titanium carbide, hard ceramics, and tungsten carbide. is a mixture of
During the sonication and low temperature heating-quenching process,
1) Add the metal powder embedded with the reinforcing body to alcohol to obtain a mixed liquid, sonicate for 5 min to 60 min, vacuum dry the mixed liquid to obtain a dry powder M, and dry powder M is 400 to A step of sieving through a 600-mesh sieve to obtain a sieved material C, which is a metal powder from which the reinforcement on the primary surface has been removed;
2) After heat-treating the sieved material C obtained in step 1 at 150 to 300° C. for 30 to 60 minutes under vacuum conditions, place it in liquid nitrogen and heat-treat it for 5 to 10 minutes. to obtain a slurry, sonicate for 10-30 minutes, vacuum-dry the slurry, obtain a dry powder N, sift the dry powder N through a 400-600 mesh sieve, and embed the reinforcement only inside a step of obtaining a sieved material D that is a metal powder that has been filtered, wherein the sieved material D is a preliminary material;
including,
A method for preparing a metal material or a metal composite material, characterized by: The method for preparing a metal material or metal composite material according to claim 1 , wherein the carbon material is at least one of 0-dimensional, 1-dimensional, 2-dimensional and 3-dimensional carbon materials. 3. The metal material according to claim 2, wherein the carbon material is a mixture of one or more of granular graphite, carbon fibers, and carbon particles after pulverization of carbon fibers in an arbitrary ratio. Or a method for preparing metal composites. The carbon material is carbon short fibers after degumming, and as a method for preparing the carbon short fibers after degumming, the short carbon fiber bundle is heated to 650 to 800° C. under a protective atmosphere and heat-retained for 20 to 90 minutes. , obtaining short carbon fibers after degumming. 4. The method for preparing a metal material or metal composite material according to claim 3 , wherein the carbon material is a carbon material coated with phenol-formaldehyde resin. The method for preparing a metallic material or metallic composite material according to claim 1, characterized in that said matrix metal A is at least one of copper, aluminum, titanium and nickel. The metal material or metal according to any one of claims 1 to 6 , wherein the mass ratio of the preliminary material and the phenol formaldehyde resin powder is 20 to 99.5:0.5 to 2. Methods of preparing composite materials. When the raw material contains the particle phase B, the mass ratio of the preliminary material, the phenol-formaldehyde resin powder and the particle phase B is 20 to 99.5:0.5 to 2:0.5 to 78. A method for preparing a metal material or metal composite material according to any one of claims 1 to 6 , characterized in that After cold-pressing the mixed material after mixing, a green compact is obtained, and then sintered under a protective atmosphere or under pressure in a vacuum or a protective atmosphere to obtain a carbon/metal composite material, or the mixed powder is directly hot pressing to obtain a carbon/metal composite,
The press pressure in the cold press molding process is 200 to 600 MPa, the holding pressure time is 20 to 30 s, the temperature in the compact sintering process is 60% to 80% of the melting point of the matrix metal, and the heat retention time is 0. .5 to 3 h, the pressure is 0 to 1 MPa,
The unit pressure in the hot pressing process is 200 to 600 MPa, the temperature is 60% to 80% of the melting point of the matrix metal, and the heat and pressure holding time is 2 to 90 minutes. A method for preparing a metallic material or metallic composite material according to any one of claims 1 to 3. 7. The method for preparing a metal material or metal composite material according to any one of claims 1 to 6 , characterized in that the obtained carbon/metal composite material has a density of 99% or more.

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