CN109518032B - Preparation method of carbon particle reinforced metal matrix composite material - Google Patents
Preparation method of carbon particle reinforced metal matrix composite material Download PDFInfo
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Abstract
The invention relates to a preparation method of a carbon particle reinforced metal matrix composite material, belonging to the technical field of metal material preparation. The degumming short carbon fiber and phenolic resin powder are subjected to high energy to obtain metal powder in which carbon particles and phenolic resin are uniformly embedded, then the metal powder is subjected to ultrasonic treatment and drying treatment to obtain metal powder in which surface carbon is removed and carbon and phenolic resin powder are embedded, and then the metal powder, the phenolic resin powder and other components are mixed and pressed and sintered to obtain the carbon particle reinforced metal matrix composite. The invention successfully solves the problem that the interface sintering of the metal powder embedded with carbon particles is not dense in the sintering process, realizes that the mechanical property and the wear resistance of the designed and prepared metal composite material are greatly improved on the premise that the metal powder is dense in the sintering process, and has simple preparation process and low cost.
Description
Technical Field
The invention relates to a metal matrix composite material, in particular to a preparation method of a carbon particle reinforced metal matrix composite material.
Background
The carbon particle (carbon fiber, graphite and the like) reinforced metal matrix composite material has the advantages of high electrical and thermal conductivity, good toughness and corrosion resistance of metal, high toughness of carbon fiber, lubricating property of graphite and the like, and is widely applied to the fields of heat conduction materials, conductive materials, friction materials and the like.
In recent years, researchers have made a lot of researches to improve the mechanical properties and high-temperature oxidation resistance of composite materials, mainly focusing on the improvement of the wettability of a carbon/metal interface, the reduction of the wettability of the interface with carbon by adding carbon, such as plating metal on the surface of carbon, adding other alloy elements into the metal, the improvement of the oxidation resistance of materials by using artificial particles and carbon fibers, and the promotion of the reduction of a metal oxide film layer by coating treatment of phenolic resin, thereby promoting the sintering diffusion of metal.
Publication No. CN108018506A discloses a short carbon fiber modified high-friction composite material, which is characterized in that: the raw materials of the short carbon fiber modified high-friction composite material comprise the following components: 1-3 wt.% of short carbon fiber is coated and cured by resin; the dispersion strengthening copper powder of the nano oxide is more than or equal to 15wt percent; in the nano-oxide dispersion strengthened copper powder, the nano-oxide is generated in situ. The short carbon fiber and the copper powder are subjected to resin coating-curing treatment and ball milling to prepare pre-alloyed powder, and then the pre-alloyed powder is mixed with other component powder and is pressed and sintered to prepare the short carbon fiber modified high-friction composite material. However, this method may have a problem that a small amount of carbon fibers exposed outside the copper particles may hinder sintering diffusion between the copper particles, resulting in possible non-dense sintering.
The inventor researches and discovers that the degummed carbon fiber or the phenolic resin coated carbon fiber and the soft metal are subjected to ball milling to obtain metal powder in which carbon particles or short carbon fibers are uniformly embedded. The Chinese invention patent CN108018506A discloses a short carbon fiber modified high-friction composite material, which comprises the following raw materials: 1-3 wt% of short carbon fiber subjected to resin coating-curing treatment; the dispersion strengthening copper powder of the nano oxide is more than or equal to 15wt percent; in the nano-oxide dispersion strengthened copper powder, the nano-oxide is generated in situ. The short carbon fiber and the copper powder are subjected to resin coating-curing treatment and ball milling to prepare pre-alloyed powder, and then the pre-alloyed powder is mixed with other component powder and is pressed and sintered to prepare the short carbon fiber modified high-friction composite material. However, this method may have a problem that a small amount of carbon fibers exposed outside the copper particles may hinder sintering diffusion between the copper particles, resulting in possible non-dense sintering. Such as plating of transition metals with carbon surfaces or formation of metal carbides through oxidation or dip-cracking chemical combination, can affect the performance of the carbon particles or the carbon fibers themselves.
Disclosure of Invention
In order to solve the technical defects of poor compactness and unsatisfactory performances of the existing carbon particle reinforced metal matrix composite material, the invention provides a method for preparing the carbon particle reinforced metal matrix composite material, and aims to prepare the carbon particle reinforced metal matrix composite material (the invention is also called as the composite material for short) with good compactness and excellent performances such as strength, toughness and the like.
The carbon material can be used for enhancing the performance of the metal matrix composite material, but the carbon material and the metal phase often have interface obstruction, the enhancement effect of the carbon material is difficult to fully exert, the carbon material and part of matrix metal are compounded in advance to obtain carbon-embedded metal powder, and then the carbon-embedded metal powder is sintered with the matrix metal, so that the performance of the obtained carbon particle enhanced metal can be enhanced, but the improvement degree is limited. The inventor of the present invention, through intensive research, first found that the main reason is that the surface of the carbon-embedded metal powder inevitably exposes the carbon material to block sintering diffusion during sintering, resulting in sintering incompactness. Based on the technical problem discovered by the invention initiatively, the invention innovatively provides a method for obtaining metal composite powder in which carbon particles and submicron-scale phenolic resin powder are uniformly embedded by adding fine phenolic resin powder in a ball milling process, removing carbon materials on the surface of the carbon-embedded metal composite powder by utilizing ultrasonic treatment combined with a low-temperature heating-chilling process, finally supplementing and adding micron-scale phenolic resin powder in a mixing process, and realizing nearly fully-compact sintering by utilizing a reducing atmosphere formed by high-temperature cracking during phenolic resin sintering to improve the performance of the composite material obtained by sintering. The method comprises the following specific steps:
the invention relates to a preparation method of a carbon particle reinforced metal matrix composite, which comprises the steps of ball-milling a carbon material, phenolic resin powder I and matrix metal A (also called metal A) to obtain metal powder (also called ball grinding material) with carbon particles and phenolic resin powder embedded on the surface and in the metal powder; carrying out ultrasonic treatment on the ball-milled metal powder and combining a low-temperature heating-chilling process to remove superfine carbon particles on the surface of the ball-milled metal powder to obtain a spare material;
and mixing the raw materials including the standby material, the phenolic resin powder II and optionally the particle phase B, pressing and sintering to obtain the carbon particle reinforced metal matrix composite.
According to the invention, phenolic resin powder, a carbon material and metal A powder are subjected to ball milling treatment to obtain metal composite powder in which carbon particles and phenolic resin powder are uniformly embedded, and then the carbon embedded on the surface of the metal powder is effectively removed by utilizing ultrasonic treatment combined with a low-temperature heating-chilling process, and the high reducing atmosphere formed during high-temperature pyrolysis of the phenolic resin powder is combined, so that the sintering among metal powder particles is promoted, the structure of the carbon is effectively protected, and the characteristics of the carbon are exerted to the greatest extent.
The method innovatively embeds the carbon material and the phenolic resin fine powder into the matrix metal in advance through ball milling, and then innovatively removes the carbon exposed outside the metal of the metal composite powder by using a low-temperature heating-chilling process, so that the sintering diffusion of the metal composite powder in the matrix metal is effectively improved, and the sintering compactness is obviously improved. The preparation method provided by the invention obtains the metal matrix composite material with high strength, high toughness, high temperature resistance and good wear resistance on the premise of realizing the sintering densification of the metal powder, and has the advantages of simple preparation process and low cost.
Preferably, the carbon material is at least one of a zero-dimensional, one-dimensional, two-dimensional, and three-dimensional carbon material. More preferably, the carbon material is one or more of particulate graphite, carbon fiber and carbon particles obtained by crushing carbon fiber, and is mixed according to any proportion.
As a further preferable mode, the carbon material is short carbon fiber. The length of the short carbon fiber is preferably 1-5 mm; the diameter is preferably 6 to 8 μm.
Most preferably, the carbon material is degummed short carbon fiber.
The preparation method of the degummed short carbon fiber comprises the following steps: under a protective atmosphere; heating the short carbon fiber bundle to 650-800 ℃, and carrying out heat preservation treatment for 20-90 min; obtaining the degummed short carbon fiber. The length of the degummed short carbon fiber is preferably 1-5 mm; the diameter is preferably 6 to 8 μm.
In the present invention, the base metal A may be any base metal material known to those skilled in the art of alloy that can be used to prepare carbon reinforced composites.
Preferably, the oxide of the base metal A is hardly used and/or is available as H2Reducing in one or more reducing atmospheres in CO; and/or, the oxide of the base metal A may also be H2Reducing in one or more reducing atmospheres in CO; preferably, the base metal A is at least one of aluminum, titanium, zirconium, copper, iron, nickel, chromium, manganese and silver; more preferably at least one of copper, aluminum, titanium and nickel.
The particle size of the phenolic resin powder I is less than or equal to 100 micrometers, and preferably 10-80 micrometers.
The volume ratio of the metal powder A to the carbon material to the phenolic resin powder I is 80-99: 0.01-1: 1-19; further preferably 80 to 90:0.5 to 1:9 to 9.5. The proportion is controlled, so that the performance of the prepared composite material can be further improved, and particularly, the mechanical property and the wear resistance are obviously improved.
Preferably, the carbon material, the phenolic resin powder I and the matrix metal A are ball-milled, and the carbon material and the phenolic resin powder I are embedded into the matrix metal in advance, so that metal powder with uniformly distributed carbon material and phenolic resin powder I can be obtained, sintering is further promoted, and the performance of the prepared composite material is improved; and the performance of the prepared composite material can be further obviously improved by matching with the ultrasonic treatment innovatively provided by the invention.
According to the invention, the carbon material, the phenolic resin powder I and the matrix metal A are subjected to high-energy ball milling to obtain the ball milling material, and the ball milling material is metal powder with carbon particles and phenolic resin powder embedded on the surface and in the interior.
Preferably, the ball milling rotating speed is 220-350 r/min.
Preferably, in the ball milling, the mass ratio of the total mass of the carbon material, the phenolic resin powder I and the matrix metal A to the grinding balls is 1: 5-8.
Preferably, the time is at least 6 h.
The particle size of the metal powder obtained by ball milling is preferably 40-300 μm.
The invention also innovatively carries out ultrasonic treatment combined with low-temperature heating-chilling treatment on the metal powder obtained by ball milling, and aims to remove carbon embedded in the metal powder.
Preferably, the ultrasonic treatment combined with the low-temperature heating-chilling process comprises the following steps: and (3) carrying out ultrasonic treatment on the metal powder obtained by ball milling, carrying out heat treatment on the material subjected to ultrasonic treatment at the temperature of 150-300 ℃, chilling (quenching) the material subjected to heat treatment in liquid nitrogen, and carrying out ultrasonic treatment on the material subjected to chilling treatment to obtain the spare material with surface carbon removed.
Further preferably, the ultrasonic treatment is combined with the low-temperature heating-chilling process step:
1) adding metal powder obtained by ball milling into alcohol to obtain a mixed solution, carrying out ultrasonic treatment for 5-60 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, wherein the oversize product C is the metal powder with primary surface carbon removed;
2) carrying out heat treatment on the oversize product C obtained in the step 1) 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 dry powder N, and sieving the dry powder N through a 400-600-mesh sieve to obtain an oversize product D, wherein the oversize product D is a spare material for removing surface carbon.
Preferably, the 400-600 mesh sieves in step 1) and step 2) are selected from any one of ultrasonic stainless steel vibrating sieves, ultra-fine powder separation ultrasonic rotary vibration sieves and common vibrating sieves.
Further preferably, the temperature of the vacuum drying in the step 1) and the step 2) is 60 to 80 ℃.
Preferably, the solvent is an aqueous solution of ethanol.
Preferably, the frequency of the ultrasonic wave is preferably 20 to 50 KHz.
In the invention, the standby material and the phenolic resin powder II are mixed and then pressed and sintered; or mixing the standby material with the phenolic resin powder and the particle phase B, and then pressing and sintering to obtain the carbon particle reinforced metal matrix composite.
The particle size of the phenolic resin powder II is less than or equal to 300 mu m; preferably 50 to 200 μm.
The particle phase B is one or more of iron, chromium, tungsten, silicon carbide, granular graphite, flaky graphite, iron-chromium alloy, aluminum oxide, silicon carbide, titanium carbide, hard ceramic and tungsten carbide which are mixed according to any proportion.
The particle size of the particle phase B is preferably 10-400 μm.
According to the invention, the particle size standby material, the phenolic resin powder II and the optionally contained particle phase B are prepared by a physical mixing method, so that the compactness and the strength of the sintered material can be further improved.
Preferably, the volume ratio of the spare material, the phenolic resin powder II and the particle phase B is 49-99.5: 0.01-1: 0 to 50. The proportion is controlled, so that the performance of the prepared composite material can be further improved, and particularly, the mechanical property and the wear resistance are obviously improved.
Preferably, when the particle phase B is not added in the mixing process, the mass ratio of the standby material to the phenolic resin powder II is 49-99.5: 0.01 to 1.
Preferably, when the particle phase B is added in the mixing process, the volume ratio of the standby material, the phenolic resin powder II and the particle phase B is 49-99.5: 0.01-1: 0.05 to 50.
And sintering the mixed material by adopting the existing method according to the characteristics of the matrix metal to prepare the composite material.
Preferably, the present invention is a carbon particle reinforced metal matrix composite; cold press molding the mixed material to obtain a pressed blank, and sintering under the pressure condition of protective atmosphere or vacuum or protective atmosphere to obtain the carbon/metal composite material; or directly hot-pressing the mixed powder to obtain the carbon particle reinforced metal matrix composite.
The pressing pressure in the cold press molding process is 200-600 MPa, and the pressure maintaining time is 20-30 s; the temperature of the green compact in the sintering process is 60-80% of the melting point of the base metal, the heat preservation time is 0.5-3 h, and the pressure is 0-1 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 preservation and pressure maintaining time is 2-90 min.
The temperature in the cold press molding process is, for example, room temperature, preferably 15 to 35 ℃.
When the designed composite material is a carbon particle reinforced metal matrix composite material, the more preferable preparation method comprises the following steps:
step one
Ultrasonic treatment of carbon and phenolic resin powder embedded metal composite powder;
the ultrasonic treatment process of the carbon and phenolic resin powder embedded metal composite powder (carbon embedded metal composite powder) comprises the following steps:
adding surface and internal carbon-embedded and phenolic resin powder metal composite powder (carbon-embedded metal composite powder) into alcohol to obtain mixed liquid, carrying out ultrasonic treatment for 10-30 min, carrying out vacuum drying on the mixed liquid to obtain dried powder M, and sieving the dried powder M through a 400-600-mesh sieve to obtain oversize product C, wherein the oversize product C is the metal composite powder with primary surface carbon removed;
and then carrying out heat treatment on the obtained oversize product C 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, and sieving the dried powder N through a sieve of 400-600 meshes to obtain an oversize product D, wherein the obtained oversize product D is metal composite powder only internally embedded in carbon and phenolic resin powder.
Step two
Distributing the ultrasonically treated carbon-embedded metal composite powder, the phenolic resin powder and the particle phase B component powder obtained in the first step according to a design group, and uniformly mixing to obtain mixed powder;
step three
Pressing and refrigerating the mixed powder obtained in the step two to obtain a pressed compact, and sintering under one of a protective atmosphere, a vacuum condition and a protective atmosphere pressurization condition to obtain the carbon particle reinforced metal matrix composite; or directly hot-pressing the mixed powder to obtain the carbon particle reinforced metal matrix composite.
When the designed composite material is a carbon particle reinforced metal matrix composite material, in the second step, during material mixing, stirring the materials uniformly through a V-shaped mixer; the stirring speed of the V-shaped mixer is 45-120r/min, and the mixing time is 2-8 h.
When the designed composite material is a carbon particle reinforced metal matrix composite material, in the fourth step, the pressing pressure of cold pressing is 200-600 MPa, and the pressure maintaining time is 20-30 s;
when the designed composite material is a carbon particle reinforced metal matrix composite material, the sintering temperature is 60-80% of the melting point of the matrix metal, the heat preservation time is 0.5-3 h, and the pressure is 0-1 MPa;
when the designed composite material is a carbon particle reinforced metal matrix 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 maintaining time is 2-90 min.
In the preferred scheme of the invention, the carbon material and the phenolic resin powder are innovatively embedded into the matrix metal in advance by ball milling, then the carbon exposed outside the metal of the carbon-embedded metal composite powder is innovatively removed by combining ultrasonic treatment with a low-temperature heating-chilling process, so that the sintering diffusion of the carbon-embedded metal composite powder in the matrix metal is effectively improved, the sintering compactness is obviously improved, finally the phenolic resin powder is added in the material mixing process, and the nearly fully dense sintering is realized by utilizing the reducing atmosphere formed by high-temperature cracking during the sintering of the superfine submicron phenolic resin in the metal composite powder and the phenolic resin supplemented during the material mixing. The preparation method provided by the invention obtains the metal matrix composite material with high strength, high toughness, high temperature resistance and good wear resistance on the premise of realizing the sintering densification of the metal powder, and has the advantages of simple preparation process and low cost.
According to the preparation method of the carbon particle reinforced metal matrix composite material, the density of the obtained carbon particle reinforced metal matrix composite material is more than or equal to 98.9%. The optimized product can reach 99.8%.
The invention firstly tries to obtain the high-performance carbon particle reinforced metal matrix composite material by adopting metal composite powder in which carbon particles are reinforced and phenolic resin is uniformly embedded to replace metal powder as a raw material, combining ultrasonic treatment with a low-temperature heating-chilling process, adding phenolic resin powder during mixing, and pressing and sintering.
The principle and the advantages of the invention are as follows:
in terms of raw material selection, metal powder is replaced by metal composite powder enhanced by carbon particles and uniformly embedded by phenolic resin, so that the dispersion of carbon in a matrix is remarkably improved, and the sintering densification of the interior of the metal powder is promoted by utilizing reducing gas generated by cracking of the phenolic resin at high temperature. The carbon types comprise artificial graphite, granular graphite, carbon fibers, carbon particles formed by crushing the carbon fibers and the like, and in the traditional mixing process, the carbon is easy to spontaneously agglomerate, so that the distribution in a matrix is extremely uneven, and the mechanical property and the frictional wear property of the material are reduced. If carbon can be added by pre-forming carbon reinforced metal powder raw materials through processes such as ball milling and the like, the dispersion degree of the carbon in a matrix is obviously improved, so that the overall performance is obviously improved.
And (4) selecting a surface decarbonization process. The sintering densification of the powder is mainly carried out by the atomic diffusion among the particles, and an oxide film and a heterogeneous phase on the surface of the metal particles become an interface for hindering the sintering, so that the sintering densification among the powder particles is reduced. Although the carbon particles reinforce the metal powder instead of the metal powder can achieve uniform dispersion of carbon in the matrix, the carbon exposed outside the metal powder also hinders sintering diffusion between the metal particles. Although surface carbon can be removed by oxidation in an aerobic environment, metal oxidation can be caused, for example, alumina formed by aluminum powder cannot be reduced by hydrogen and is difficult to reduce by CO, and for the metal powder, the process of removing carbon and reducing on the oxidized surface cannot be adopted, so that the carbon on the surface of the metal powder can be removed by combining ultrasonic treatment and a low-temperature heating-chilling process, and the subsequent pressing and sintering of the powder are facilitated.
Adding phenolic resin powder during mixing. The inventor proposes a saturated solution formed by mixing phenolic resin and alcohol in Chinese patent CN108018506A, which is used for impregnating graphite, carbon fiber and other substances, can effectively remove functional groups on the surface of the graphite, has a particularly high wetting speed, and modifies the graphite surface through a resin coating layer formed after low-temperature curing, thereby protecting the carbon fiber structure. However, the thickness of the cured coating layer reaches hundreds of micrometers or even millimeters, and although gas is generated by cracking at high temperature during sintering, the size of carbon remained by cracking is thicker (reaching submicron level), so that the porosity of the material is improved. Therefore, the patent proposes that phenolic resin powder replaces phenolic resin saturated solution, micron or submicron phenolic resin powder is added during ball milling and mixing respectively to be uniformly distributed in a mixture, and when the mixture is sintered at high temperature after pressing, the powder is uniformly cracked in the material and H is released2Reducing gas such as CO, etc., effectively reducing the oxide film on the surface of the metal, promoting the sintering of the metal, and the residual carbon generated by cracking the phenolic resin powder is activated carbon and is porousThin, easy to contact with H2Reaction to produce reduced CH4A gas. At the moment, most of the added phenolic resin powder is cracked into gas, and the rest part is decomposed into a nano-scale thick carbon film; forming a riveting structure that metal atoms penetrate through the carbon film when the carbon film is thin by utilizing diffusion of carbon and metal atoms; thereby providing necessary conditions for realizing the nearly fully dense sintering of the metal.
The preparation process is simple and low in cost, and the preparation of the composite material taking the carbon reinforced metal powder as the raw material is realized only by combining ultrasonic treatment with a low-temperature heating-chilling process and adding the phenolic resin powder during mixing.
The morphology of the carbon enhanced metal powder is shown in fig. 2. The composite material prepared by directly using carbon reinforced metal powder as a raw material without any treatment is shown in figure 3. The carbon reinforced and phenolic resin embedded metal composite powder was subjected to ultrasonic treatment and drying treatment to prepare a composite material as shown in fig. 4. As can be seen from fig. 2, the surface of the carbon-reinforced metal powder is exposed to a large amount of carbon, which hinders the subsequent sintering. As can be seen from fig. 3, the carbon-reinforced metal powder is directly used as a raw material without any treatment, and a large number of pores are present in the mixed material, pressed material and sintered material due to the obstruction of the carbon interface. As can be seen from FIG. 4, the ultrasonic treatment combined with the low-temperature heating-chilling process realizes the sintering densification among the metal particles, so that the metal matrix composite material with the densification degree of more than 99% is obtained, and the obtained composite material has excellent and uniform performance and good market prospect.
Drawings
FIG. 1 is a flow chart of the preparation of a carbon particle reinforced metal matrix composite according to the present invention;
FIG. 2 is a SEM image of carbon particle enhanced copper powder;
FIG. 3 is a composite material prepared by directly using carbon particle reinforced copper powder as a raw material without any treatment;
FIG. 4 shows a copper-based composite material prepared by subjecting copper powder in which carbon particles are reinforced and phenolic resin powder are uniformly embedded to ultrasonic treatment, drying, mixing with phenolic resin powder, and finally pressing and sintering.
Fig. 1 shows a process for preparing a carbon particle reinforced metal matrix composite material according to the present invention, which specifically comprises: firstly, degumming carbon fibers, phenolic resin powder I and matrix metal powder A are subjected to ball milling to obtain metal powder in which carbon particles are reinforced and the phenolic resin powder is uniformly embedded, the obtained powder is subjected to ultrasonic treatment combined with low-temperature heating-chilling to remove carbon, then conventional mixing is carried out on the powder, the phenolic resin powder and hard particles, and finally pressing-sintering treatment is carried out to obtain the carbon particle reinforced metal-based composite material.
As can be seen from fig. 2 and 3, the surface of the carbon-reinforced metal powder has a large amount of carbon exposed, and the carbon-reinforced metal powder is directly used as a raw material without any treatment, so that sintering densification between metal powder particles cannot be achieved.
As can be seen from fig. 4, the ultrasonic treatment with optimized parameters, the low-temperature heating-chilling process and the addition of the phenolic resin powder during ball milling and mixing are combined, so that the sintering densification among the metal particles is realized, and the metal matrix composite material with uniformly distributed carbon particles and small porosity is obtained.
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
Step (1): in example 1, commercially available short carbon fibers were used, and the diameter of the short carbon fibers was 7 μm and the length thereof was 1 mm. And (3) carrying out heat treatment on the short carbon fiber bundle at 700 ℃ for 50min under the inert atmosphere or vacuum condition to obtain the carbon fiber bundle. Mixing short carbon fiber bundles, phenolic resin powder I and copper powder according to the volume ratio of 9: 1: 90, ball milling, wherein the particle size of the electrolytic copper powder is 150 mu m, and the particle size of the phenolic resin powder I is 80 mu m to obtain mixed powder; the condition parameters of the ball milling are as follows: the rotating speed is 280r/min, the ball milling time is 6h, the ball milling balls are stainless steel balls and hard alloy balls, and 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). Then sieving with a 400-mesh sieve, taking the undersize as a standby material (shown in an SEM picture in figure 2), wherein the mass ratio of the sum of the mass of the degummed short fiber, the phenolic resin powder I and the electrolytic copper powder to the ball grinding ball is 1: 6.
Step (2): after ball milling, mixing copper powder embedded with superfine carbon powder and phenolic resin powder with alcohol, performing ultrasonic treatment for 120min (ultrasonic frequency is 25KHz), maintaining the temperature of the solution at room temperature, performing vacuum drying on the solution after ultrasonic treatment at 60 ℃, sieving by using an ultrasonic rotary vibration sieve, wherein the minimum mesh number of the sieve is 400 meshes, and retaining oversize products, namely metal powder removed by primary surface carbon. And then, carrying out vacuum heat preservation on the powder at 150 ℃ for 30min, directly placing the powder in liquid nitrogen for heat preservation for 10min, then mixing the powder with alcohol, carrying out ultrasonic treatment for 20min, finally carrying out vacuum drying on the ultrasonic solution at 60 ℃, and carrying out screening treatment by using an ultra-fine powder separation ultrasonic rotary vibration sieve to obtain the copper powder only internally embedded with ultra-fine carbon and phenolic resin powder.
And (3): mixing copper powder only containing internal superfine carbon and phenolic resin powder with phenolic resin powder II according to the volume ratio of 99:1, wherein the particle size of the phenolic resin powder II is 200 mu m, and mixing in a V-shaped mixer to obtain mixed powder. And then carrying out cold pressing on the 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 ℃ under the pressure of 0.9MPa, the heating rate and the cooling rate of a furnace are both 10-15 ℃/min, a sample of the example 1 is obtained, the appearance of the prepared copper-based composite material is shown in figure 4, the density of the composite material is 99%, and the bending strength is 521 MPa.
Comparative example 1
Other conditions of this comparative example 1 were the same as those of example 1 except that in the step (1), the phenolic resin powder I was not added, the carbon particle-embedded copper powder prepared by ball milling was directly subjected to room temperature pressing-hydrogen sintering, and the phenolic resin powder II was not added during the pressing. Other process steps and parameter control were the same as in example 1. The SEM image of the resulting material is shown in FIG. 3.
The comparative example was not subjected to ultrasonic treatment and low temperature-chilling treatment, and was not added with the phenolic resin powder I and the phenolic resin powder II. The prepared copper-based composite material is shown in figure 3, the porosity is as high as 10%, no diffusion sintering is carried out among metal particles, and the bending strength is 380 MPa.
Comparative example 2
Other conditions of this comparative example 2 were the same as those of example 1 except that the phenolic resin powder I was not added in step (1) and the phenolic resin powder II was not added in step (3). The other operations were the same as in example 1.
According to the comparative example, carbon particles prepared by ball milling of degummed short carbon fibers and copper powder are embedded into the copper powder, and after ultrasonic treatment and low-temperature-chilling treatment, room-temperature pressing-hydrogen sintering is directly carried out without adding phenolic resin powder I and phenolic resin powder II. The porosity of the prepared copper-based composite material is 5%, and the bending strength is 505 MPa.
Comparative example 3
Comparative example 3 the other conditions were the same as in example 1 except that no phenolic resin powder I was added in step (1). The other operations were the same as in example 1.
According to the method, carbon particles prepared by ball milling of degummed short carbon fibers and copper powder are embedded into the copper powder, and then phenolic resin powder II is added to mix, and then room temperature pressing-hydrogen sintering is directly carried out without adding phenolic resin powder I. The porosity of the prepared copper-based composite material is 2.5%, and the bending strength is 518 MPa.
Example 2
Step (1): in example 2, commercially available short carbon fibers were used, and the diameter of the short carbon fibers was 8 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 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 150 mu m, and mixing short carbon fiber bundles, phenolic resin powder I (the particle size is 50 mu m) and the electrolytic nickel powder according to the volume ratio of 9.5: 0.5: 90, ball milling is carried out, 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 fiber, the phenolic resin powder I and the electrolytic nickel copper powder to the ball milling ball is 1: 6.
Step (2): after ball milling, mixing the prepared nickel powder with the short carbon fibers embedded inside and on the surface with alcohol, performing ultrasonic treatment for 100min (ultrasonic frequency is 30KHz), maintaining the temperature of the solution at room temperature, performing vacuum drying on the ultrasonic solution at 60 ℃, sieving by using an ultrasonic rotary vibrating sieve, wherein the minimum mesh number of the sieve is 400 meshes, and retaining oversize products, namely the metal powder with the primary surface carbon removed. And then, carrying out vacuum heat preservation on the powder at 180 ℃ for 30min, directly placing the powder in liquid nitrogen for 10min, then mixing the powder with alcohol, carrying out ultrasonic treatment for 20min, finally carrying out vacuum drying on the ultrasonic solution at 60 ℃, and carrying out screening treatment by using an ultra-fine powder separation ultrasonic rotary vibration sieve to obtain the nickel powder only internally embedded with carbon particles and phenolic resin powder.
And (3): mixing nickel powder only internally embedded with carbon particles and phenolic resin powder with phenolic resin powder II according to a volume ratio of 99:1, wherein the particle size of the phenolic resin powder II is 150 mu m, and mixing in a V-shaped mixer to obtain mixed powder. And then carrying out cold pressing on the mixed powder at room temperature, wherein the pressing pressure is 480MPa, 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 pressure is 0.6MPa, the temperature rising rate and the temperature lowering rate of a furnace are both 10-15 ℃/min, and the sample of the example 2 is obtained. The compactness of the nickel-based composite material is 98.9 percent, and the tensile strength is 1280 MPa.
Comparative example 4
Other conditions of this comparative example 4 are the same as those of example 2, except that in step (1), the phenolic resin powder I is not added, the carbon particle-embedded nickel powder prepared by ball milling is directly subjected to room temperature pressing-hydrogen sintering, and the phenolic resin powder II is not added during the pressing. Other process steps and parameter control were the same as in example 2.
In the comparative example, phenolic resin powder I is not mixed in the ball milling process, and the carbon particles prepared by ball milling are embedded into the nickel powder, and are not subjected to ultrasonic treatment and low-temperature-chilling treatment, and are not mixed with phenolic resin powder II, and room-temperature pressing-hydrogen sintering is directly carried out. The porosity of the prepared copper-based composite material is up to 12%, and the copper-based composite material is not diffused and sintered among metal particles, and the bending strength is 745 MPa.
Comparative example 5
The same as in example 2, except that the phenolic aldehyde resin powder I was not added in step (1) and the phenolic aldehyde resin powder II was not added in step (3). The other operations were the same as in example 2.
Other conditions of the comparative example were the same as those of example 2, except that only carbon particles prepared by ball-milling degummed short carbon fibers and nickel powder were embedded in the nickel powder, and after ultrasonic treatment and low-temperature-chilling treatment, room-temperature pressing-hydrogen sintering was directly performed without adding the phenol-formaldehyde resin powder I and the phenol-formaldehyde resin powder II. The porosity of the prepared nickel-based composite material is 6%, and the bending strength is 1140 MPa.
Comparative example 6
The same as in example 1 except that the phenolic aldehyde resin powder I was not added in step (1). The other operations were the same as in example 2.
Other conditions of the comparative example 6 are the same as those of the example 2, except that only carbon particles prepared by ball milling the degummed short carbon fibers and the nickel powder are embedded into the nickel powder, and after ultrasonic treatment and low-temperature-chilling treatment are carried out, the mixture of the phenolic resin powder II is added, and room-temperature pressing-hydrogen sintering is directly carried out without adding the phenolic resin powder I. The porosity of the prepared nickel-based composite material is 3%, and the bending strength is 1187 MPa.
Comparative example 7
The same as in example 1 except that the phenolic novolak resin powder II was not added in step (3). The other operations were the same as in example 2.
Other conditions of the comparative example 7 are the same as those of the example 2, except that the carbon particles and the phenolic resin powder prepared by ball milling the degummed short carbon fibers, the phenolic resin powder I and the nickel powder are embedded into the nickel powder, and after ultrasonic treatment and low-temperature-chilling treatment, room-temperature pressing-hydrogen sintering is directly carried out without adding the phenolic resin powder II. The porosity of the prepared nickel-based composite material is 2.8%, and the bending strength is 1208 MPa.
Comparative example 8
The other conditions of the comparative example 8 are the same as those of the example 2, except that the phenolic resin powder II is not added in a powder form, the phenolic resin powder II and alcohol are mixed to prepare a phenolic resin alcohol saturated solution, the carbon particles and the phenolic resin powder are embedded into the nickel powder to be subjected to ultrasonic treatment and low-temperature chilling treatment (the nickel powder embedded with the carbon particles and the phenolic resin powder in the step (2)), the carbon particles and the phenolic resin powder are immersed in the phenolic resin alcohol saturated solution for 2 hours, the solution is dried at 100 ℃ for 2 hours, the solution is crushed and then is subjected to cold pressing at room temperature, 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 pressure is sintered at 1000 ℃ for 2 hours, the pressure is 0.8MPa, and the heating rate and the cooling rate of a furnace are both 10-15 ℃/. The compactness of the nickel-based composite material is 95.7 percent, and the tensile strength is 1052 MPa.
Example 3
Step (1): in example 3, commercially available short carbon fibers were used, and the diameter of the short carbon fibers was 8 μm and the length thereof was 2 mm. Keeping the temperature of 720 ℃ for 60min under the vacuum condition, and carrying out degumming treatment; then adding the short carbon fiber bundles, the phenolic resin powder I and the aluminum powder into ball milling equipment together with atomized Al-9.6 wt% Zn-2.5 wt% Mg-2.2 wt% Cu-0.16 wt% Zr alloy powder with the particle size of 150 mu m and phenolic resin powder I with the particle size of 80 mu m for high-energy ball milling, wherein the short carbon fiber bundles, the phenolic resin powder I and the aluminum powder are mixed according to the volume ratio of 9: 1: 90, ball milling is carried out, 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 fiber, the phenolic resin powder I and the aluminum powder to the ball milling ball is 1: 6.
Step (2): after ball milling, mixing the prepared aluminum powder with carbon particles and phenolic resin powder embedded inside and on the surface with alcohol, performing ultrasonic treatment for 120min (ultrasonic frequency is 28KHz), maintaining the temperature of the solution at room temperature, performing vacuum drying on the ultrasonic solution at 60 ℃, and sieving by using an ultrasonic rotary vibrating sieve to retain oversize products, namely the metal powder with primary surface carbon removed. And then, carrying out vacuum heat preservation on the powder at 200 ℃ for 30min, directly placing the powder in liquid nitrogen for heat preservation for 10min, then mixing the powder with alcohol, carrying out ultrasonic treatment for 20min, finally carrying out vacuum drying on the ultrasonic solution at 60 ℃, and carrying out screening treatment by using an ultra-fine powder separation ultrasonic rotary vibration sieve to obtain the aluminum powder only internally embedded with carbon fibers and phenolic resin powder.
And (3): taking 180 mu m aluminum powder only embedded with carbon particles and phenolic resin powder, taking phenolic resin powder II and silicon carbide powder according to the volume ratio of 90:1:9, taking the powder, wherein the particle size of the phenolic resin powder II is 100 mu m, and the particle size of the silicon carbide is 90 mu m, and mixing in a V-shaped mixer to obtain mixed powder. The obtained mixed powder is hot-pressed at 490 ℃ under the protection of nitrogen atmosphere, the pressing pressure is 500MPa, and the hot-pressing time is 0.5h, so that the aluminum matrix composite material is obtained, the density is 99%, and the bending strength is 823 MPa.
Comparative example 9
The same as example 3, except that in step (1), no phenolic resin powder I was added, the ball-milled material was not subjected to ultrasonic treatment and low-temperature-chilling treatment, and no phenolic resin powder II was added during pressing. Other process steps and parameter control were the same as in example 3.
Other conditions of the comparative example 9 are the same as those of the example 3, except that the carbon particles prepared by ball milling are directly embedded into the aluminum powder to be subjected to room temperature pressing-hydrogen sintering, and after being mixed with silicon carbide, the mixture is mixed in a V-shaped mixer to obtain mixed powder, ultrasonic treatment and low temperature-chilling treatment are not performed, and no phenolic resin powder I and no phenolic resin powder II are added. The obtained mixed powder is hot-pressed at 490 ℃ under the protection of nitrogen atmosphere, the pressing pressure is 500MPa, the hot-pressing time is 0.5h, and the aluminum matrix composite material is obtained, the compactness is only 89%, and the bending strength is 657 MPa.
Comparative example 10
The same as in example 3, except that the phenolic aldehyde resin powder I was not added in step (1) and the phenolic aldehyde resin powder II was not added in step (3). The other operations were the same as in example 3.
Other conditions of the comparative example 10 are the same as those of the example 3, except that the carbon particles prepared by ball milling the degummed short carbon fibers and the aluminum powder are embedded into the aluminum powder, ultrasonic treatment and low-temperature-chilling treatment are carried out, and room-temperature pressing-hydrogen sintering is directly carried out after the carbon particles are mixed with 2% of silicon carbide, without adding the phenolic resin powder I and the phenolic resin powder II. The porosity of the prepared aluminum-based composite material is 9%, and the bending strength is 689 MPa.
Comparative example 11
The same as in example 3 except that the phenolic novolak resin powder II was not added in step (3). The other operations were the same as in example 3.
Other conditions of the comparative example 11 are the same as those of the example 3, except that the carbon particles prepared by ball milling the degummed short carbon fibers, the phenolic resin powder I and the aluminum powder are embedded into the aluminum powder, ultrasonic treatment and low-temperature-chilling treatment are carried out, and room-temperature pressing-hydrogen sintering is directly carried out after the carbon particles are mixed with 2% of silicon carbide, without adding the phenolic resin powder II. The porosity of the prepared aluminum matrix composite material is 8%, and the bending strength is 712 MPa.
Example 4
Step (1): in this example 4, commercially available short carbon fibers degummed at 700 ℃ for 60min, reduced iron powder with a particle size of 120 μm, and phenolic resin powder I with a particle size of 80 μm are used as ball milling raw materials, and the volume percentages of the carbon fibers, the reduced iron powder, and the phenolic resin powder I are 9.5: 92: 0.5. the diameter of the short carbon fiber is 6 mu m, the length of the short carbon fiber is 2mm, the short carbon fiber and the hard alloy are added into ball milling equipment for high-energy ball milling, the rotating speed is 250r/min, the ball milling time is 6h, the ball-material ratio is 6:1, the ball milling balls are stainless steel balls and hard alloy balls, and the ball diameter is 3 mm-10 mm (the mass ratio of the ball milling ball diameter to the ball milling ball diameter is 4:8:11:20:12:8:6:1, 4mm, 5mm, 6mm, 7mm, 8mm and 9mm is 4:8: 20: 8: 6.
Step (2): after ball milling, mixing the prepared iron powder with the superfine carbon and phenolic resin powder embedded inside and on the surface with alcohol, performing ultrasonic treatment for 120min (ultrasonic frequency is 28KHz), maintaining the temperature of the solution at room temperature, performing vacuum drying on the ultrasonic solution at 60 ℃, and screening by using an ultrasonic rotary vibration screen, wherein oversize products, namely the metal powder with the primary surface carbon removed, are reserved. And then, preserving the vacuum of the powder at 200 ℃ for 30min, directly placing the powder in liquid nitrogen for 10min, then mixing the powder with alcohol, carrying out ultrasonic treatment for 20min, finally, drying the ultrasonic solution at 60 ℃ in vacuum, and carrying out screening treatment by using an ultra-fine powder separation ultrasonic rotary vibration sieve to obtain the iron powder only internally embedded with the ultra-fine carbon and the phenolic resin powder.
And (3): and (2) mixing iron powder only internally embedded with superfine carbon and phenolic resin powder with phenolic resin powder II according to the volume ratio of 99:1, mixing the materials, wherein the granularity of the phenolic resin powder II is 120 mu m, and mixing the materials in a V-shaped mixer to obtain mixed powder. And (3) cold pressing the obtained mixed powder at room temperature, wherein the pressing pressure is 550MPa, the pressure maintaining time is 20s, the prepared iron alloy pressed blank is subjected to pressure sintering under the vacuum protection, the iron alloy pressed blank is sintered for 2 hours at 1050 ℃, the pressure is 0.3MPa, the heating rate and the cooling rate of a furnace are both 10-15 ℃/min, and the iron-based composite material is obtained, the density is 99%, and the tensile strength is 857 MPa.
Comparative example 12
The same as example 4, except that in step (1), no phenolic resin powder I was added, the ball-milled material was not subjected to ultrasonic treatment and low-temperature-chilling treatment, and no phenolic resin powder II was added during pressing. Other process steps and parameter control were the same as in example 4.
The comparative example 12 is otherwise identical to example 4 except that the ball-milled ultrafine carbon-embedded iron powder was directly subjected to room-temperature press-vacuum pressure sintering in the same process as in example 4 without ultrasonic treatment and low-temperature-chilling treatment, and without the addition of the phenolic resin powder I and the phenolic resin powder II. The porosity of the prepared iron-based composite material is up to 12%, and the tensile strength is 610 MPa.
Comparative example 13
The same as in example 4 except that the phenolic aldehyde resin powder I was not added in step (1) and the phenolic aldehyde resin powder II was not added in step (3). The other operations were the same as in example 4.
Other conditions of this comparative example 13 are the same as those of example 4 except that carbon particles prepared by ball-milling degummed short carbon fibers and reduced iron powder were embedded in the iron powder, and after ultrasonic treatment and low-temperature-chilling treatment, room-temperature pressing-hydrogen sintering was directly performed without adding the phenol aldehyde resin powder I and the phenol resin powder II. The porosity of the prepared iron-based composite material is 8%, and the bending strength is 710 MPa.
Comparative example 14
Same as example 4 except that, in step (3), the phenolic novolak powder II was not added. The other operations were the same as in example 4.
Other conditions of this comparative example 14 are the same as those of example 4, except that the degummed short carbon fiber, the phenolic resin powder I and the reduced iron powder were ball-milled to prepare carbon particles, and the carbon particles were embedded in the aluminum powder, and after the ultrasonic treatment and the low-temperature-chilling treatment, the room-temperature pressing-hydrogen sintering was directly performed without adding the phenolic resin powder II. The porosity of the prepared iron-based composite material is 2%, and the tensile strength is 749 MPa.
Example 5
Step (1): in this example 5, commercially available short carbon fibers degummed at 800 ℃ for 30min, titanium alloy powder (Ti-6 wt% Al-2.8 wt% Sn-3.5 wt% Zr-0.75 wt% Nb-0.35 wt% Si) having a particle size of 50 μm, and phenolic resin powder I having a particle size of 50 μm were used as ball-milling raw materials (the volume ratio of the titanium alloy powder to the phenolic resin powder I to the degummed short carbon fibers was 80: 1: 19). The diameter of the short carbon fiber is 6 micrometers, the length of the short carbon fiber is 2mm, the short carbon fiber and the short carbon fiber are added into ball milling equipment for high-energy ball milling, the rotating speed is 250r/min, the ball milling time is 12 hours, the ball milling ball is a hard alloy ball, the ball diameter is 3 mm-9 mm (the mass ratio of the ball milling ball diameter to 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 degumming short fiber, the phenolic resin powder I and the titanium alloy powder to the ball milling ball is 1: 8.
Step (2): after ball milling, mixing the prepared titanium alloy powder with the superfine carbon and phenolic resin powder embedded inside and on the surface with alcohol, performing ultrasonic treatment for 120min (ultrasonic frequency is 28KHz), maintaining the temperature of the solution at room temperature, performing vacuum drying on the ultrasonic solution at 60 ℃, and screening by using an ultrasonic rotary vibration screen, wherein oversize products, namely the metal powder with the primary surface carbon removed, are reserved. And then, preserving the vacuum temperature of the powder at 400 ℃ for 30min, directly placing the powder in liquid nitrogen for 10min, then mixing the powder with alcohol, carrying out ultrasonic treatment for 20min, finally, carrying out vacuum drying on the ultrasonic solution at 60 ℃, and carrying out screening treatment by using an ultra-fine powder separation ultrasonic rotary vibration sieve to obtain the titanium alloy powder only internally embedded with the ultra-fine carbon and phenolic resin powder.
And (3): titanium powder only internally embedded with superfine carbon and phenolic resin powder II are mixed according to the volume ratio of 99:1, mixing the materials, wherein the granularity of the phenolic resin powder II is 150 mu m, and mixing the materials in a V-shaped mixer to obtain mixed powder. 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 titanium-based composite material pressed compact is sintered in vacuum and sintered at 1350 ℃ for 2h, and the heating rate and the cooling rate of a furnace are both 15 ℃/min, so that the titanium-based composite material is obtained, the density is 98.8%, and the tensile strength is 1310 MPa.
Comparative example 15
The same as example 5, except that in step (1), no phenolic resin powder I was added, the ball-milled material was not subjected to ultrasonic treatment and low-temperature-chilling treatment, and no phenolic resin powder II was added during pressing. Other process steps and parameter control were the same as in example 5.
Other conditions of this comparative example 15 are the same as those of example 5 except that the ball-milled ultrafine carbon-embedded titanium powder was directly subjected to room-temperature press-vacuum sintering, and the process was the same as example 6 without ultrasonic treatment and low-temperature-chilling treatment, and without adding the phenolic resin powder I and the phenolic resin powder II. The porosity of the prepared titanium-based composite material is up to 11%, and the tensile strength is 950 MPa.
Comparative example 16
The same as in example 5 except that the phenolic aldehyde resin powder I was not added in step (1) and the phenolic aldehyde resin powder II was not added in step (3). The other operations were the same as in example 5.
Other conditions of the comparative example 16 are the same as those of example 5, except that carbon particles prepared by ball-milling degummed short carbon fibers and titanium alloy powder are embedded in the titanium alloy powder, and room temperature pressing-hydrogen sintering is directly performed after ultrasonic treatment and low temperature-chilling treatment without adding phenolic resin powder I and phenolic resin powder II. The porosity of the prepared titanium-based composite material is 10%, and the bending strength is 1010 MPa.
Comparative example 17
The same as in example 5 except that the phenolic novolak resin powder II was not added in step (3). The other operations were the same as in example 5.
Other conditions of the comparative example 17 are the same as those of the example 5, except that carbon particles prepared by ball-milling degummed short carbon fibers, the phenolic resin powder I and the titanium alloy powder are embedded in the titanium alloy powder, and after ultrasonic treatment and low-temperature-chilling treatment, room-temperature pressing-hydrogen sintering is directly performed without adding the phenolic resin powder II. The density of the prepared titanium-based composite material is 98%, and the tensile strength is 1240 MPa.
Example 6
The process for preparing the iron powder to be embedded with only the fine carbon and phenolic resin powders as well as the mixing and pressing process of this example 6 are the same as those of example 4 except that the sintering process is different. The sintering process is that the pressed compact is pressed and sintered under the vacuum protection, sintered for 2h at 750 ℃, and then sintered for 2h after being heated to 1100 ℃, the heating rate and the cooling rate of a furnace are both 10-15 ℃/min, the pressure is 0.5MPa, and the superfine carbon particle reinforced iron alloy is obtained, the density is 99.2%, and the tensile strength is 865 MPa.
From the data, the carbon particle reinforced metal matrix composite material prepared by the material disclosed by the invention is excellent in mechanical property and wear resistance.
Claims (6)
1. A method for preparing a carbon particle reinforced metal matrix composite; the method is characterized in that: ball-milling the carbon material, phenolic resin powder I and matrix metal A to obtain metal powder with carbon particles and phenolic resin powder embedded on the surface and inside; carrying out ultrasonic treatment on the metal powder obtained by ball milling and combining a low-temperature heating-chilling process to remove carbon particles on the surface of the metal powder to obtain a spare material;
mixing raw materials including a standby material, phenolic resin powder II and optionally a particle phase B, pressing and sintering to obtain a carbon particle reinforced metal matrix composite;
the matrix metal A is at least one of aluminum, titanium, zirconium, copper, iron, nickel, chromium, manganese and silver;
the particle size of the phenolic resin powder I is less than or equal to 100 mu m;
the volume ratio of the metal powder A to the carbon material to the phenolic resin powder I is 80-99: 0.01-1: 1-19;
the ultrasonic treatment combines the process steps of low-temperature heating-chilling:
1) adding metal powder obtained by ball milling into alcohol to obtain a mixed solution, carrying out ultrasonic treatment for 5-60 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, wherein the oversize product C is the metal powder with primary surface carbon removed;
2) carrying out heat treatment on the oversize product C obtained in the step 1) 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 dry powder N, and sieving the dry powder N through a 400-600-mesh sieve to obtain an oversize product D, wherein the obtained oversize product D is a spare material for removing surface carbon;
the frequency of the ultrasonic wave is 20-50 KHz;
the particle size of the phenolic resin powder II is less than or equal to 300 mu m;
the granular phase B is one or more of iron, chromium, tungsten, granular graphite, flaky graphite, iron-chromium alloy, aluminum oxide, silicon carbide, titanium carbide, hard ceramic and tungsten carbide which are mixed according to any proportion;
the volume ratio of the spare material to the phenolic resin powder II to the particle phase B is 49-99.5: 0.01-1: 0 to 50;
when the particle phase B is not added in the mixing process, the mass ratio of the standby material to the phenolic resin powder II is 49-99.5: 0.01 to 1; when the particle phase B is added in the mixing process, the volume ratio of the standby material, the phenolic resin powder II and the particle phase B is 49-99.5: 0.01-1: 0.05 to 50;
cold press molding the mixed material to obtain a pressed blank, and sintering under the pressure condition of protective atmosphere or vacuum or protective atmosphere to obtain the carbon particle reinforced metal matrix composite; or directly hot-pressing the mixed powder to obtain the carbon/metal composite material;
the pressing pressure in the cold press molding process is 200-600 MPa, and the pressure maintaining time is 20-30 s; the temperature of the green compact in the sintering process is 60-80% of the melting point of the base metal A, the heat preservation time is 0.5-3 h, and the pressure is 0-1 MPa;
the unit pressure in the hot pressing process is 200-600 MPa, the temperature is 60-80% of the melting point of the base metal A, and the heat preservation and pressure maintaining time is 2-90 min.
2. A method for producing a carbon particle-reinforced metal matrix composite material according to claim 1; the method is characterized in that: the carbon material is at least one of zero-dimensional, one-dimensional, two-dimensional and three-dimensional carbon materials.
3. A method for producing a carbon particle-reinforced metal matrix composite material according to claim 2; the method is characterized in that: the carbon material is at least one of artificial graphite particles, carbon fibers, fiber carbon particles and graphite particles.
4. A method for producing a carbon particle-reinforced metal matrix composite material according to claim 3; the method is characterized in that: the carbon material is short carbon fiber; the length is 1-5 mm; the diameter is 6 to 8 μm.
5. A method for producing a carbon particle-reinforced metal matrix composite material according to claim 4; the method is characterized in that: the carbon material is degummed short carbon fiber;
the preparation process of the degummed short carbon fiber comprises the following steps: and (3) carrying out heat treatment on the short carbon fiber bundle at 650-800 ℃ for 20-90 min under an inert atmosphere or vacuum condition to obtain the carbon fiber bundle.
6. A method for producing a carbon particle-reinforced metal matrix composite material as claimed in any one of claims 1 to 5; the method is characterized in that: the ball milling rotating speed is 220-350 r/min;
in the ball milling, the mass ratio of the total mass of the carbon material, the phenolic resin powder I and the matrix metal A to the grinding ball is 1: 5-8;
the time is at least 6 h.
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