CN108788132B - In-situ reaction preparation method of copper-carbon composite material - Google Patents
In-situ reaction preparation method of copper-carbon composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 79
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 99
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000011258 core-shell material Substances 0.000 claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000011812 mixed powder Substances 0.000 claims abstract description 24
- 238000007731 hot pressing Methods 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 10
- 239000010439 graphite Substances 0.000 claims abstract description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 30
- 229910052786 argon Inorganic materials 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 238000011068 loading method Methods 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 7
- 229940112669 cuprous oxide Drugs 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 230000004584 weight gain Effects 0.000 claims description 4
- 235000019786 weight gain Nutrition 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 30
- 239000011159 matrix material Substances 0.000 abstract description 7
- 238000006479 redox reaction Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 26
- 239000002245 particle Substances 0.000 description 11
- 238000000465 moulding Methods 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000005551 mechanical alloying Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002783 friction material Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 239000012691 Cu precursor Substances 0.000 description 1
- 241000227287 Elliottia pyroliflora Species 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
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- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/001—Starting from powder comprising reducible metal compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/058—Mixtures of metal powder with non-metallic powder by reaction sintering (i.e. gasless reaction starting from a mixture of solid metal compounds)
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Abstract
A method for preparing a copper-carbon composite material by in-situ reaction. The method selects copper powder with a core-shell structure to be mixed with carbon powder to obtain mixed powder, and prepares the carbon-copper composite material by hot-pressing and sintering at high temperature. The invention adopts Cu-Cu with a core-shell structure2Mixing O with graphite powder, and sintering at high temperature under hot pressing2In-situ oxidation-reduction reaction is carried out between O and graphite, so that firm combination between copper and graphite is realized, the influence of a two-phase interface on the conductivity of the material is reduced to the maximum extent, and the mechanical property of the composite material is greatly improved. Compared with the copper-carbon composite material obtained by directly mixing and sintering copper powder and carbon powder, the density of the copper-carbon composite material prepared by the method is improved by 2-6%, and the compressive strength is improved by 20-60%. The method has simple process, and the prepared carbon-copper composite material matrix and the carbon two phases are distributed uniformly and combined well, and have excellent electrical and mechanical properties and frictional wear properties.
Description
Technical Field
The invention discloses an in-situ reaction preparation method of a carbon-copper composite material. Belongs to the technical field of powder metallurgy.
Background
The copper-carbon composite material has the advantages of good electric and heat conducting properties, small friction coefficient, low wear rate and the like, is a novel functional material, and is applied to the fields of electric contact materials, friction materials, oil-containing bearings and mechanical part materials.
The main preparation method of the copper-carbon composite material comprises the following three steps: mechanical alloying, powder metallurgy, liquid phase impregnation. Because the density difference between graphite and copper is huge, the composite powder with uniform dispersion is difficult to prepare by a mechanical alloying method, and simultaneously, carbon tends to be attached to the surface of metal particles in the mechanical alloying process, so that the metal and the metal phase cannot be directly contacted in the subsequent sintering process, and the comprehensive performance of the material is difficult to improve. The conventional powder metallurgy method directly mixes copper powder and graphite powder for sintering to prepare a blank, but the product density is not high, and the bonding strength between copper and carbon is not high. The liquid phase impregnation method can prepare large-size copper-carbon composite materials, but because the thermal expansion coefficients of copper and carbon are greatly different and the infiltration angles of the copper and the carbon are very large, the defects of infirm combination of the copper and the carbon, hole generation and the like are easy to occur in the cooling process after infiltration.
CN 104894424B discloses a preparation method of a self-lubricating copper-carbon pantograph composite material, which adopts Gasar porous copper as a precursor, presses a mixture of a binder and graphite into the precursor, and prepares the copper-carbon composite material through a die-casting and sintering process, but the carbon content and the material performance are limited by the porosity and strength of a porous copper precursor; CN 102694329a discloses a process of mixing, pressing and sintering a carbon material, a binder and a copper-plated carbon material, wherein the addition of the binder can help the material to be formed, but can greatly affect the conductivity and friction performance of the material, so that the material has high resistivity, is fragile and has poor lubricity. CN 105880284a discloses a method for preparing a high-conductivity copper-carbon composite material, in which graphite powder is uniformly spread on a copper plate, and then a repeated rolling process is performed to prepare the composite material.
Disclosure of Invention
Aiming at the defects of the existing copper-carbon composite material, the copper-carbon composite material is prepared by the redox reaction and vacuum hot-pressing sintering method, so that the affinity between a matrix and carbon can be greatly improved, and the copper-carbon composite material with excellent comprehensive performance is obtained.
The invention provides a high-performance copper-carbon composite material and a preparation method thereof.
The invention relates to a copper-carbon composite material in-situ reaction preparation method, which comprises the following steps:
the first step is as follows: mixing material
Uniformly mixing copper powder with a core-shell structure and carbon powder to obtain mixed powder; the core-shell structure copper powder is core-shell structure copper powder with a pure copper core and cuprous oxide on the surface;
the second step is that: vacuum hot pressing sintering
Cold pressing the mixed powder obtained in the first step, loading into a vacuum hot press die, and vacuumizing to 10 DEG-3Pa above, heating to 550 ℃ along with 450-.
According to the in-situ reaction preparation method of the copper-carbon composite material, the particle size range of the copper powder with the core-shell structure is 30-300 microns, preferably 50-100 microns, the particle size range of the carbon powder is 25-300 microns, preferably 30-80 microns, the particle size ratio of the graphite powder to the copper powder is controlled to be 0.5-1, and the mass ratio of the graphite powder in the mixed powder is more than or equal to 11.1%.
The invention relates to a copper-carbon composite material in-situ reaction preparation method, wherein carbon powder is selected from one of artificial graphite, crystalline flake graphite and carbon fiber.
The invention relates to an in-situ reaction preparation method of a copper-carbon composite material, which is characterized in that copper powder with a core-shell structure and carbon powder are mixed by a V-shaped stirrer or a ball mill, and alcohol accounting for 1.0-1.5% of the mass of the mixed powder is added during stirring or ball milling.
According to the in-situ reaction preparation method of the copper-carbon composite material, the temperature rise speed in the vacuum hot-pressing sintering process is 5-15 ℃/min, and preferably 8-12 ℃/min; heating to 480-520 ℃, applying 20-50MPa pressure to the pressed compact, keeping the temperature for 1-4h, then heating to 880-920 ℃, and keeping the pressure for 0.5-2 h.
The invention relates to an in-situ reaction preparation method of a copper-carbon composite material, wherein copper powder with a core-shell structure is prepared by adopting the following oxidation reaction method:
heating the copper powder to 350 ℃ under the protection of argon, stopping introducing the argon, introducing compressed air instead, wherein the air flow is 0.5-1.5L/min, keeping the temperature for 10-20 minutes, stopping introducing the air, introducing the argon again, heating to 900 ℃ under 850 ℃ and keeping the temperature for 20-40 minutes, and cooling to room temperature along with the furnace to obtain the copper powder with the core-shell structure.
The invention relates to an in-situ reaction preparation method of a copper-carbon composite material, wherein in the material mixing process, the addition amount of carbon powder in mixed powder is determined by calculation according to a formula (1):
the mass fraction of the carbon content in the copper-carbon composite material is p, if the weight gain of the copper powder with the core-shell structure before and after oxidation is delta w, the total mass of the copper powder with the core-shell structure is wCuAnd then according to the reaction process of the carbon powder and oxygen in the copper powder with the core-shell structure, calculating the addition amount of the carbon powder as follows:
wc＝wCu·p/(1-p)+0.75Δw (1)；
or the like, or, alternatively,
the addition amount of the carbon powder in the mixed powder is determined according to the sum of the following two carbon amounts:
a first part, the carbon amount determined by the product of the weight of the prepared copper-carbon composite material and the mass ratio p of carbon in the copper-carbon composite material;
a second part: carbon and oxygen in the copper powder with the core-shell structure are subjected to oxidation reaction and converted into carbon oxide.
The invention relates to a method for preparing a copper-carbon composite material by in-situ reaction, which is characterized in that carbon and oxygen in copper powder with a core-shell structure are subjected to oxidation reaction to be converted into carbon oxide, and the consumed carbon amount is determined according to the following method:
and measuring the oxygen content in the copper powder with the core-shell structure by adopting a weight gain method, and calculating the required carbon amount according to an oxidation reaction equation.
The oxidation temperature of the copper powder is 250-350 ℃, the oxidation time is 10-15 minutes, and the air flow is 0.5-1.5L/min.
In the invention, carbon and oxygen in the copper powder with the core-shell structure are subjected to oxidation reaction and converted into CO or CO2。
The carbon content of the copper-carbon composite material prepared by the method is 10-80%.
Advantages and positive effects of the invention
The surface layer of the core-shell structure copper powder prepared by the method is a layer of uniform cuprous oxide, a pure copper matrix is still kept inside the core-shell structure copper powder, and in the preparation process, oxygen is diffused into the copper matrix through the following two steps: (1) reacting with surface copper to produce copper oxide, (2) further diffusing oxygen to the copper core in an argon environment, and further reacting the surface copper oxide with the copper core to produce cuprous oxide; thereby, the interface between the cuprous oxide layer and the inner copper core remains well bonded. The copper-carbon composite material prepared by the core-shell structure copper powder can effectively improve the bonding strength between copper and carbon.
Adopts Cu-Cu with a core-shell structure2Mixing O with graphite powder, and sintering at high temperature under hot pressing2In-situ oxidation-reduction reaction is carried out between O and graphite, so that firm combination between copper and graphite is realized, the influence of a two-phase interface on the conductivity of the material is reduced to the maximum extent, and the mechanical property of the composite material is greatly improved. Compared with the copper-carbon composite material obtained by directly mixing and sintering copper powder and carbon powder, the density of the copper-carbon composite material prepared by the method is improved by 2-6%, and the compressive strength is improved by 20-60%.
The method has simple process, and the prepared carbon-copper composite material matrix and the carbon two phases are distributed uniformly and combined well, and have excellent electrical and mechanical properties and frictional wear properties.
Drawings
FIG. 1 shows core-shell copper powder with pure copper core and cuprous oxide surface prepared in example 1.
Fig. 2 is an SEM photograph of the copper-carbon composite material prepared in example 1.
Fig. 3 is an SEM photograph of the copper-carbon composite material prepared in comparative example 1.
As can be seen from fig. 1: the surface layer of the core-shell structure copper powder prepared by the method is a layer of uniform cuprous oxide, a pure copper matrix is still kept inside the core-shell structure copper powder, and the interface of the core-shell structure copper powder still keeps good combination as oxygen enters the copper matrix through diffusion. The copper-carbon composite material prepared by the core-shell structure copper powder can effectively improve the bonding strength between copper and carbon.
As can be seen from fig. 2: embodiment 1 of the invention adopts a locally oxidized core-shell structure Cu-Cu2The carbon in the copper-carbon composite material prepared from the O powder is distributed more uniformly and finely, and the copper and the carbon are combined more tightly;
as can be seen from fig. 3: in comparative example 1 of the present invention, the composite material obtained by directly mixing copper powder and graphite powder, hot-pressing and sintering the copper powder and the graphite powder has micropores at the interface of copper and carbon, and the interface bonding is poor.
Detailed Description
Example 1
Copper powder with the particle size range of 50-100 mu m and graphite powder with the particle size range of 30-80 mu m are selected as raw materials, and the copper-carbon composite material is prepared according to the following steps of (1) oxidizing the copper powder: putting 80g of copper powder in a tubular furnace, introducing argon for protection, heating to 300 ℃, stopping introducing argon, introducing compressed air with the air flow of 1L/min, preserving heat for 15 minutes, stopping introducing air, introducing argon again for protection, heating to 850 ℃, preserving heat for 30 minutes, cooling and cooling to obtain the partially oxidized core-shell structure Cu-Cu2O powder (shown in figure 1), and the weight is increased by 2.0 g; (2) mixing powder: the Cu-Cu obtained in the step (1)2Mixing O powder with 21.5g of graphite powder, adding alcohol with the total mass of 1.0%, and mixing powder in a V-shaped stirrer or a ball mill for 30 minutes; (3) vacuum hot pressing: cold press molding the mixed powder obtained in the step (2), then loading the mixed powder into a copper sleeve, then loading the copper sleeve into a vacuum hot press mold, and vacuumizing to 10 DEG-3And Pa, heating to 500 ℃ at the speed of 15 ℃/min, pressurizing to 30MPa, preserving heat for 2h, heating to 900 ℃ at the speed of 10 ℃/min, maintaining the pressure for 2h, and cooling to obtain the copper-carbon composite material with the carbon volume fraction of 50%.
Comparative example 1
For comparison, the same batch of copper powder and graphite powder is adopted to prepare a copper-carbon composite material comparison sample according to the following steps: (1) mixing powder: mixing copper powder and powder graphite according to the volume ratio of 1:1, adding alcohol with the total mass of 1.0%, and mixing powder in a V-shaped stirrer or a ball mill for 30 minutes; (2) vacuum hot pressing: cold press molding the mixed powder obtained in the step (1), then loading the mixed powder into a copper sleeve, then loading the copper sleeve into a vacuum hot press mold, and vacuumizing to 10 DEG-3And Pa, heating to 500 ℃ at the speed of 15 ℃/min, pressurizing to 30MPa, preserving heat for 2h, heating to 900 ℃ at the speed of 10 ℃/min, maintaining the pressure for 2h, and cooling to obtain a copper-carbon composite material comparison sample with the carbon volume fraction of 50%.
The microstructure photographs of the two copper-carbon composites are shown in fig. 2 and 3, respectively. Thus, the core-shell structure Cu-Cu adopting local oxidation2Prepared from powder OThe carbon in the copper-carbon composite material is distributed more uniformly and finely, and the copper and the carbon are combined more tightly (figure 1); the composite material obtained by directly mixing copper powder and graphite powder, hot-pressing and sintering can have micropores at the interface of copper and carbon, and the interface bonding is poor (figure 2). The two copper-carbon composite material property pairs are shown in table 1. Thus, the core-shell structure Cu-Cu adopting local oxidation2The copper-carbon composite material prepared from the O powder has higher density, and has more excellent mechanical property and conductivity. The method can greatly improve the structure and the performance of the copper-carbon composite material.
TABLE 1 two copper-carbon composite material performance tables
Example 2
Copper powder with the particle size range of 50-100 mu m and graphite powder with the particle size range of 30-80 mu m are selected as raw materials, and the copper-carbon composite material is prepared according to the following steps of (1) oxidizing the copper powder: putting 80g of copper powder in a tubular furnace, introducing argon for protection, heating to 300 ℃, stopping introducing argon, introducing compressed air with the air flow of 1L/min, preserving heat for 15 minutes, stopping introducing air, introducing argon again for protection, heating to 850 ℃, preserving heat for 30 minutes, cooling and cooling to obtain the partially oxidized core-shell structure Cu-Cu2O powder, the weight is increased by 2.0 g; (2) mixing powder: the Cu-Cu obtained in the step (1)2Mixing O powder with 62g of graphite powder, adding alcohol with the total mass of 1.0%, and mixing the powder in a V-shaped stirrer or a ball mill for 30 minutes; (3) vacuum hot pressing: cold press molding the mixed powder obtained in the step (2), then loading the mixed powder into a copper sleeve, then loading the copper sleeve into a vacuum hot press mold, and vacuumizing to 10 DEG-3And Pa, heating to 500 ℃ at the speed of 15 ℃/min, pressurizing to 30MPa, preserving heat for 2h, heating to 900 ℃ at the speed of 10 ℃/min, maintaining the pressure for 2h, and cooling to obtain the copper-carbon composite material with the carbon volume fraction of 75%.
Comparative example 2
For comparison, the same batch of copper powder and graphite powder is adopted to prepare a copper-carbon composite material comparison sample according to the following steps: (1) mixing powder: will be provided withMixing copper powder and powdered graphite according to the volume ratio of 1:3, adding alcohol with the total mass of 1.0%, and mixing powder in a V-shaped stirrer or a ball mill for 30 minutes; (2) vacuum hot pressing: cold press molding the mixed powder obtained in the step (1), then loading the mixed powder into a copper sleeve, then loading the copper sleeve into a vacuum hot press mold, and vacuumizing to 10 DEG-3And Pa, heating to 500 ℃ at the speed of 15 ℃/min, pressurizing to 30MPa, preserving heat for 2h, heating to 900 ℃ at the speed of 10 ℃/min, maintaining the pressure for 2h, and cooling to obtain a copper-carbon composite material comparison sample with the carbon volume fraction of 75%.
The two copper-carbon composite property pairs are shown in table 2. Therefore, when the carbon content reaches 75% by volume, the mechanical property and the conductivity of the composite material obtained by directly mixing, hot-pressing and sintering the copper powder and the graphite powder are greatly reduced; and adopts a locally oxidized core-shell structure Cu-Cu2The copper-carbon composite material prepared from the O powder can still keep good density, mechanical property and conductivity. This shows that the method of the patent has great advantages in preparing copper-carbon composite materials with high carbon content.
TABLE 2 two tables for copper-carbon composite material
Example 3
Copper powder with the particle size range of 50-100 mu m and graphite powder with the particle size range of 30-80 mu m are selected as raw materials, and the copper-carbon composite material is prepared according to the following steps of (1) oxidizing the copper powder: putting 120g of copper powder in a tubular furnace, introducing argon for protection, heating to 300 ℃, stopping introducing argon, introducing compressed air with the air flow of 1L/min, preserving heat for 15 minutes, stopping introducing air, introducing argon again for protection, heating to 850 ℃, preserving heat for 30 minutes, cooling and cooling to obtain the partially oxidized core-shell structure Cu-Cu2O powder, the weight is increased by 3.0 g; (2) mixing powder: the Cu-Cu obtained in the step (1)2Mixing O powder with 47.8g of graphite powder, adding alcohol with the total mass of 1.0%, and mixing powder in a V-shaped stirrer or a ball mill for 30 minutes; (3) vacuum hot pressing: cold-pressing the mixed powder obtained in the step (2) to form a mixture, and filling copper into the mixtureSleeving, loading the copper sleeve into a vacuum hot press die, and vacuumizing to 10 DEG- 3Pa, heating to 500 ℃ at a speed of 15 ℃/min, pressurizing to 30MPa, keeping the temperature for 2h, heating to 900 ℃ at a speed of 10 ℃/min, maintaining the pressure for 2h, and cooling to obtain the copper-carbon composite material with the carbon volume fraction of 60%, the density of 99.5%, the compressive strength of 118MPa, the conductivity of 18.0% IACS, the friction coefficient of only 0.17, and the wear rate of 1.2 multiplied by 10-10mm3N-1m-1. Therefore, the copper-carbon composite material prepared by the method has excellent mechanical property, conductivity and frictional wear property.
Example 4
Copper powder with the particle size range of 50-100 mu m and graphite powder with the particle size range of 30-80 mu m are selected as raw materials, and the copper-carbon composite material is prepared according to the following steps of (1) oxidizing the copper powder: putting 120g of copper powder in a tubular furnace, introducing argon for protection, heating to 300 ℃, stopping introducing argon, introducing compressed air with the air flow of 1L/min, preserving heat for 15 minutes, stopping introducing air, introducing argon again for protection, heating to 850 ℃, preserving heat for 30 minutes, cooling and cooling to obtain the partially oxidized core-shell structure Cu-Cu2O powder, the weight is increased by 3.0 g; (2) mixing powder: the Cu-Cu obtained in the step (1)2Mixing O powder with 9.8g of graphite powder, adding alcohol with the total mass of 1.0%, and mixing powder in a V-shaped stirrer or a ball mill for 30 minutes; (3) vacuum hot pressing: cold press molding the mixed powder obtained in the step (2), then loading the mixed powder into a copper bush vacuum hot press mold, and vacuumizing to 10 DEG-3Pa, heating to 500 ℃ at the speed of 15 ℃/min, pressurizing to 30MPa, preserving heat for 2h, heating to 900 ℃ at the speed of 10 ℃/min, maintaining the pressure for 2h, and cooling to obtain the copper-carbon composite material with the carbon volume fraction of 20%, wherein the density is 99.5%, the compressive strength can reach 305MPa, and the electric conductivity can reach 58.6% IACS. The copper-carbon composite material with low carbon content prepared by the method has excellent mechanical property and electrical conductivity, is a conductive copper alloy material integrating structure and functional characteristics, and can be widely applied to the fields of electric contact materials, friction materials, oil-containing bearings and mechanical part materials.
Claims (8)
1. A copper-carbon composite material in-situ reaction preparation method comprises the following steps:
the first step is as follows: mixing material
Uniformly mixing copper powder with a core-shell structure and carbon powder to obtain mixed powder; the core-shell structure copper powder is core-shell structure copper powder with a pure copper core and cuprous oxide on the surface;
the copper powder with the core-shell structure is prepared by adopting the following oxidation reaction method:
heating the copper powder to 350 ℃ under the protection of argon, stopping introducing the argon, introducing compressed air instead, wherein the air flow is 0.5-1.5L/min, keeping the temperature for 10-20 minutes, stopping introducing the air, introducing the argon again, heating to 900 ℃ under 850 ℃ and keeping the temperature for 20-40 minutes, and cooling to room temperature along with the furnace to obtain the copper powder with the core-shell structure;
the second step is that: vacuum hot pressing sintering
Cold pressing the mixed powder obtained in the first step, loading into a vacuum hot press die, and vacuumizing to 10 DEG-3Pa above, heating to 550 ℃ along with 450-.
2. The in-situ reaction preparation method of the copper-carbon composite material according to claim 1, characterized by comprising the following steps: the grain diameter range of the copper powder with the core-shell structure is 30-300 mu m, the grain diameter range of the carbon powder is 25-300 mu m, and the grain diameter ratio of the carbon powder to the copper powder is controlled between 0.5-1.
3. The in-situ reaction preparation method of the copper-carbon composite material according to claim 2, characterized by comprising the following steps: the mass ratio of the carbon powder in the mixed powder is more than or equal to 11.1 percent.
4. The in-situ reaction preparation method of the copper-carbon composite material according to claim 3, characterized by comprising the following steps: the carbon powder is selected from one of artificial graphite, crystalline flake graphite and carbon fiber.
5. The in-situ reaction preparation method of the copper-carbon composite material according to claim 1, characterized by comprising the following steps: mixing the copper powder with the core-shell structure and the carbon powder by adopting a V-shaped stirrer or a ball mill, and adding alcohol accounting for 1.0-1.5% of the mass of the mixed powder during stirring or ball milling.
6. The in-situ reaction preparation method of the copper-carbon composite material according to claim 1, characterized by comprising the following steps: the temperature rise speed in the vacuum hot-pressing sintering process is 5-15 ℃/min; heating to 480-520 ℃, applying 20-50MPa pressure to the pressed compact, keeping the temperature for 1-4h, then heating to 880-920 ℃, and keeping the pressure for 0.5-2 h.
7. The in-situ reaction preparation method of the copper-carbon composite material according to any one of claims 1 to 6, characterized by comprising the following steps: in the mixing process, the adding amount of carbon powder in the mixed powder is determined by calculation according to the formula (1):
the mass fraction of the carbon content in the copper-carbon composite material ispIf the weight gain of the copper powder with the core-shell structure before and after oxidation is prepared isΔ wThe total mass of the copper powder with the core-shell structure isw Cu Then, the addition amount of the carbon powder is as follows:
w c =w Cu •p/(1-p）+0.75Δw（1）；
or the like, or, alternatively,
the addition amount of the carbon powder in the mixed powder is determined according to the sum of the following two carbon amounts:
first part, weight of copper-carbon composite material prepared and mass fraction of carbon in copper-carbon composite materialpThe carbon amount determined by the product of (a);
a second part: carbon and oxygen in the copper powder with the core-shell structure are subjected to oxidation reaction and converted into carbon oxide.
8. The in-situ reaction preparation method of the copper-carbon composite material according to claim 7, characterized by comprising the following steps: the carbon consumption for the oxidation reaction of carbon and oxygen in the copper powder with the core-shell structure to be converted into carbon oxide is determined by the following method:
and measuring the oxygen content in the copper powder with the core-shell structure by adopting a weight gain method, and calculating the required carbon amount according to an oxidation reaction equation.
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