CN110773734B - Method for refining second-phase chromium in chromium-copper refractory alloy - Google Patents
Method for refining second-phase chromium in chromium-copper refractory alloy Download PDFInfo
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Abstract
The invention discloses a method for refining second-phase chromium in a chromium-copper refractory alloy, which comprises the following steps of firstly, preparing a chromium @ graphene core-shell structure by adopting a chemical synthesis method; mixing chromium powder @ graphene core-shell structure powder with copper powder, and performing cold press molding; preparing the chromium-copper composite material by adopting an arc melting method under the protection of inert gas. The bottleneck problems of application limitation such as thinning and dispersion distribution of chromium are mainly solved through the construction of a nano core-shell structure. The size of the chromium is further refined through a rapid solidification process in a vacuum arc melting process, controllable preparation of a second phase of the chromium is realized, and the core problem in the high-chromium copper alloy preparation technology is solved. The dispersion strengthening copper alloy with high strength, high conductivity and long service life is developed. Compared with the traditional preparation method, the second-phase chromium crystal grains are refined by more than 50%, the hardness of the composite material is improved by more than 10%, and the conductivity is improved by 10-30%. The chromium-copper contact alloy with excellent comprehensive performances such as arc erosion resistance, long service life and the like is obtained.
Description
Technical Field
The invention belongs to the field of preparation of difficult-to-mix alloy materials, and particularly relates to a method for refining second-phase chromium in a chromium-copper difficult-to-mix alloy.
Background
The copper-chromium alloy has excellent mechanical property and electrical property, and the high-chromium copper alloy is a preferred material in medium-high voltage electrical equipment, and is particularly widely applied to electrical contacts and contact lines. The copper-chromium alloy has good electric contact performance mainly depending on the coordination of two components, and the copper component keeps low melting point, high electric conductivity and thermal conductivity, thereby ensuring the breaking capacity of the switch; the other component keeps high melting point, high strength and low shutoff value, and improves the compression strength, ablation resistance and fusion welding resistance of the switch material. In order to realize comprehensive superior performance of the electrical contact, the first condition is that the size of the second phase chromium component of the material is small and the second phase chromium component is uniformly distributed, but because the two liquid phases are insoluble, the phenomenon of gravity segregation coarsening or copper-chromium layering and the like of the second phase exists, and a plurality of bottleneck problems exist in the preparation process of the high-performance copper-chromium contact alloy and need to be solved urgently.
Graphene (Graphene) has a unique two-dimensional lattice structure of carbon monolayer arrangement, and the excellent thermal physical property, electrical property and mechanical property are determined by the special structure of the Graphene, wherein the conductivity is 106S/m, thermal conductivity 5000W/(m DEG C.), ultimate strength 130GPa, tensile modulus 1.01TPa and surface density 0.77 mg/m2. In addition, compared with the one-dimensional carbon nano tube, the graphene on the two-dimensional surface is easier to uniformly disperse in the preparation process, and the folds on the surface are beneficial to the interface combination of the reinforcement and the matrix. The theoretical specific surface area of the graphene reaches 2600 m2The coating material can be used as a coating material to be coated and modified with a compound or a metal to form a composite structure with excellent performance. Graphene has a wide application prospect in the fields of resin-based composite materials, metal-based composite materials, ceramic-based composite materials and rubber-based composite materials, but due to the nanostructure and chemical characteristics of graphene, a new process and a new method are urgently needed to solve the problems of the addition process of graphene, the graphene/matrix interface, the dispersion uniformity of graphene and the like.
The two-phase immiscible property in the copper-chromium alloy causes the segregation and growth of the second-phase chromium easily, the preparation process difficulty of the zirconium-chromium alloy is high, and the performance cannot reach an ideal value, so that the copper-chromium alloy is mainly used for low-chromium alloy in large-range application. In the existing patent 1 (publication No. CN 109338148A), a graphene-copper-chromium-zirconium alloy and a preparation method thereof, 0.6% -1.5% of chromium, 0.07% -0.1% of zirconium and 0.25% -1% of graphene are prepared by direct ball milling by a powder metallurgy method, mixing materials and then performing discharge plasma sintering. In the prior patent 2 (CN 110317970A), a copper-chromium-zirconium alloy is prepared by directly adding graphene oxide into 0.05-1.5% of chromium, 0.05-0.5% of zirconium, 0.05-0.15% of magnesium, 0.05-0.6% of scandium and 0.05-1.8% of graphene oxide, and then carrying out vacuum melting. The prior patent 3 (CN 109897983 a) discloses a preparation method of a modified carbon nanotube reinforced copper-chromium-based composite material, which uses CNTs and a copper-chromium alloy as raw materials to prepare an alloy by discharge plasma sintering, and has the problems of low material density and the like. In the prior patent 4 (publication No. CN 105525130A) and the prior patent 5 (publication No. 1054632388B), copper-plated graphene is added into a copper-chromium contact, so that the hardness and the arc erosion resistance of the copper-based composite material are improved.
In the above research, the hardness and conductivity of the copper-chromium alloy are improved by adding graphene, but because the graphene addition process is single, in the high-chromium (chromium >5 wt.%) copper alloy, the alloy electrical contact performance is significantly reduced due to the large chromium agglomeration size, the coarse phenomenon of the second-phase chromium is only partially reduced due to the simple powder mixing addition, and a more refined preparation process is urgently needed to solve the coarse problem of the second-phase chromium.
Disclosure of Invention
In order to solve the problems, the invention provides a method for refining second-phase chromium in a chromium-copper refractory alloy. The core-shell structure of the synthesized chromium @ graphene is designed, the chromium @ graphene is constructed through a synthesis process, the diffusion or convection path of second-phase chromium atoms in a melt is cut off to avoid the coarseness and segregation of particles generated by aggregation of the second-phase chromium atoms, the formed core-shell structure refines the second-phase chromium in a copper-chromium alloy system, and the strength, the electric conductivity and the thermal conductivity of the copper alloy are improved. According to the preparation method, the second-phase chromium is refined by the aid of the synthesized chromium @ graphene core-shell structure, and simultaneously, the graphene is introduced by the aid of the chromium @ graphene core-shell structure, so that the distribution uniformity of nano-powder in a matrix is improved, and the high-strength graphene further improves the comprehensive performance of a system.
The invention is realized by the following technical scheme:
a graphene @ chromium reinforced copper-based composite material: preparing a chromium @ graphene core-shell structure by adopting a chemical synthesis method; mixing chromium powder @ graphene core-shell structure powder and copper powder, carrying out cold press molding, and preparing by adopting an arc melting method under the protection of inert gas; the composite material comprises the following components in percentage by mass: 5-50% of chromium powder, 95-50% of copper powder and 0.001-0.005% of graphene oxide by mass.
Preferably, the purity of the chromium powder is 99.9%, and the granularity is 1000 meshes; the purity of the copper powder is 99.9 percent, and the granularity is 200 meshes; 1-5 layers of graphene oxide, and the particle size is 5-20 microns.
The preparation method of the composite material comprises the following steps:
(1) preparing a KH-550 silane coupling agent graphene oxide solution: the alcohol-water ratio is 0.5-5: 5-15%, wherein the volume fraction content of KH-550 is 0.2-1.0%, standing and hydrolyzing for 4-10 h, and adding graphene oxide and ultrasonically stirring for 30-60 min;
(2) chromium powder pretreatment: washing chromium powder with absolute ethyl alcohol and ultrasonically cleaning with deionized water twice, then layering by using a centrifugal machine, selecting chromium powder with smaller upper-layer particle size and uniform distribution, sieving by using a 1000-mesh sieve, pouring the sieved chromium powder into a pickling solution for pickling, and cleaning with deionized water again after pickling;
(3) synthesizing a chromium powder @ graphene oxide core-shell structure, pouring chromium powder into the silane coupling agent solution prepared in the step (1), and reacting at a constant temperature of 40-100 ℃ for 30-60 min; after vacuum filtration, drying the powder at 50-100 ℃ to prepare chromium powder @ graphene oxide core-shell structure powder;
(4) reducing a chromium powder @ graphene oxide core-shell structure: and (3) putting the powder obtained in the step (3) into a hydrazine hydrate solution, keeping the temperature at 85-100 ℃, magnetically stirring for 10-15 h, centrifuging to collect a product, washing for 3 times with water and methanol respectively, and carrying out vacuum freeze drying for 24-48 h to reduce the graphene oxide in the chromium powder @ graphene oxide core-shell structure, thereby preparing the chromium @ graphene core-shell structure powder.
Preferably, the pickling solution is 6.0-16.0g/L of acetic acid, and the pickling time is 5-20 s.
A method for refining second-phase chromium in chromium-copper refractory alloy comprises the following steps:
(1) carrying out ball milling and powder mixing on the chromium powder @ graphene and the copper powder prepared by the method;
(2) carrying out cold press molding on the mixed powder of copper and chromium @ graphene;
(3) and performing non-consumable arc melting and plastic processing molding on the powder block subjected to press molding to prepare the chromium refined copper-chromium alloy electrical contact composite material.
Preferably, the ball mill is pumped by a mechanical pump to be vacuumized and filled with argon for protection, the rotating speed is 150-.
Preferably, the applied pressure of the cold press molding is 100-300 MPa, and the pressure maintaining time is 15-60 s.
Preferably, the specific parameters of the arc melting are: the vacuum degree is 0.01Pa, the current is 100-500A, and the size of the tungsten electrode is 12 mm.
Advantageous effects
The reason for the reduction of the electrical conductivity and the thermal conductivity of the main properties of the electrical contact material is that the second phase chromium is coarse and is partially polymerized. The bottleneck problems of application limitation such as thinning and dispersion distribution of chromium are mainly solved through the construction of a nano core-shell structure. The size of the chromium is further refined through a rapid solidification process in a vacuum arc melting process, controllable preparation of a second phase of the chromium is realized, and the core problem in the high-chromium copper alloy preparation technology is solved. The dispersion strengthening copper alloy with high strength, high electrical conductivity, high thermal conductivity and long service life is developed. Compared with the traditional preparation method, the grain refinement is more than 50%, the hardness of the composite material is improved by more than 10%, and the conductivity is improved by 10-30%.
Drawings
FIG. 1 is an SEM image of graphene coated chromium powder;
fig. 2 effect of graphene coating and preparation process on second phase chromium refinement.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
The composite material comprises the following components in percentage by mass: 10 percent of chromium powder, 90 percent of copper powder, 99.9 percent of chromium powder purity and 1000 meshes of granularity; the purity of the copper powder is 99.9 percent, and the granularity is 200 meshes; the graphene oxide comprises 1-3 layers, the particle size is 10 microns, and the addition amount is 0.005 percent of the mass of chromium powder. Preparing a KH-550 silane coupling agent graphene oxide solution: alcohol-water ratio 0.5: 15, KH-550 content is 1.0% by volume, standingHydrolyzing for 10h, adding graphene oxide, and ultrasonically stirring for 30 min; washing chromium powder with absolute ethyl alcohol and ultrasonically cleaning with deionized water twice, then layering by using a centrifugal machine, selecting chromium powder with smaller upper-layer particle size and uniform distribution, sieving the chromium powder with a 1000-mesh sieve, pouring the sieved chromium powder into 16.0g/L acetic acid, pickling in pickling solution for 5s, and cleaning with deionized water again after pickling; reacting the silane coupling agent graphene oxide solution prepared from chromium powder at constant temperature of 100 ℃ for 30 min; after vacuum filtration, drying the powder at 100 ℃ to prepare chromium powder @ graphene oxide core-shell structure powder; and (2) putting the powder into a hydrazine hydrate solution, keeping the temperature at 85 ℃, magnetically stirring for 15h, centrifuging to collect a product, washing the product with water and methanol for 3 times respectively, and carrying out vacuum freeze drying for 48h to reduce the graphene oxide in the chromium powder @ graphene oxide core-shell structure, thereby preparing the chromium @ graphene core-shell structure powder. Carrying out ball milling and powder mixing on chromium powder, graphene and copper powder, wherein the ball milling speed is 150 r/min, the positive rotation speed is 10min, the stopping is 5min, and the ball milling time is 4 h; then cold press molding is carried out, the applied pressure of the cold press molding is 100MPa, the pressure maintaining time is 60s, the powder block body which is formed by the press molding is smelted in a non-consumable electric arc smelting device, and the vacuum degree is 2x10-3Pa, the maximum current of 500A and the tungsten electrode size of 12mm, and preparing the copper-chromium alloy electrical contact composite material with refined chromium.
Example 2
The composite material comprises the following components in percentage by mass: 20 percent of chromium powder, 80 percent of copper powder, 99.9 percent of chromium powder with the purity and 1000 meshes of granularity; the purity of the copper powder is 99.9 percent, and the granularity is 200 meshes; the number of the graphene oxide layers is 1-3, the particle size is 15 micrometers, and the addition amount of the graphene oxide layers is 0.0013% of the mass fraction of the chromium powder. Preparing a KH-550 silane coupling agent graphene oxide solution: alcohol-water ratio of 1: 10, keeping the KH-550 content at 0.2% by volume, standing for hydrolysis for 4h, adding graphene oxide, and ultrasonically stirring for 30 min; washing chromium powder with absolute ethyl alcohol and ultrasonically cleaning with deionized water twice, then layering by using a centrifugal machine, selecting chromium powder with smaller upper-layer particle size and uniform distribution, sieving the chromium powder with a 1000-mesh sieve, pouring the sieved chromium powder into 6.0g/L pickling solution for pickling for 20s, and cleaning with deionized water again after pickling; adding a silane coupling agent graphene oxide solution prepared from chromium powder into the solution, and reacting at a constant temperature of 40 DEG CThe time is 60 min; after vacuum filtration, drying the powder at 50 ℃ to prepare chromium powder @ graphene oxide core-shell structure powder; and (2) putting the powder into a hydrazine hydrate solution, keeping the temperature at 100 ℃, magnetically stirring for 15h, centrifuging to collect a product, washing the product with water and methanol for 3 times respectively, and carrying out vacuum freeze drying for 24h to reduce the graphene oxide in the chromium powder @ graphene oxide core-shell structure, thereby preparing the chromium @ graphene core-shell structure powder. Carrying out ball milling and powder mixing on chromium powder, graphene and copper powder, wherein the ball milling speed is 150 r/min, the positive rotation speed is 10min, the stopping is 5min, and the ball milling time is 4 h; then cold press molding is carried out, the applied pressure of the cold press molding is 300MPa, the pressure maintaining time is 30s, the powder block body which is formed by the press molding is smelted in a non-consumable electric arc smelting device, and the vacuum degree is 2X10-3Pa, the maximum current of 500A and the tungsten electrode size of 12mm, and preparing the copper-chromium alloy electrical contact composite material with refined chromium.
Example 3
The composite material comprises the following components in percentage by mass: 10 percent of chromium powder, 1 to 5 percent of copper powder and 1 to 5 percent of graphene oxide, wherein the addition amount of 5 microns of particle size is 0.002 percent of the mass fraction of the chromium powder. The purity of the chromium powder is 99.9 percent, and the granularity is 1000 meshes; the purity of the copper powder is 99.9 percent, and the granularity is 200 meshes; preparing a KH-550 silane coupling agent graphene oxide solution: alcohol-water ratio of 5: 15, the KH-550 content is 0.8 percent by volume, standing and hydrolyzing for 6 hours, adding graphene oxide, and ultrasonically stirring for 40 min; washing chromium powder with absolute ethyl alcohol and ultrasonically cleaning with deionized water twice, then layering by using a centrifugal machine, selecting chromium powder with smaller upper-layer particle size and uniform distribution, sieving the chromium powder with a 1000-mesh sieve, pouring the sieved chromium powder into 10.0g/L pickling solution for pickling, pickling in the pickling solution with pickling time of 10s, and cleaning again with deionized water after pickling; reacting the silane coupling agent graphene oxide solution prepared from chromium powder at a constant temperature of 70 ℃ for 50 min; after vacuum filtration, drying the powder at 80 ℃ to prepare chromium powder @ graphene oxide core-shell structure powder; and (2) putting the powder into a hydrazine hydrate solution, keeping the temperature at 100 ℃, magnetically stirring for 12h, centrifuging to collect a product, washing the product with water and methanol for 3 times respectively, and carrying out vacuum freeze drying for 30h to reduce the graphene oxide in the chromium powder @ graphene oxide core-shell structure, thereby preparing the chromium @ graphene core-shell structure powder. Mixing chromium powder @ graphene andcarrying out ball milling and powder mixing on the copper powder, wherein the ball milling rotation speed is 200 r/min, the positive rotation is carried out for 10min, the stopping is carried out for 5min, and the ball milling time is 2 h; then cold press molding is carried out, the applied pressure of the cold press molding is 300MPa, the pressure maintaining time is 40s, the powder block body which is formed by the press molding is smelted in a non-consumable electric arc smelting device, and the vacuum degree is 2X10-3Pa, the maximum current of 500A and the tungsten electrode size of 12mm, and preparing the copper-chromium alloy electrical contact composite material with refined chromium.
Example 4
The composite material comprises the following components in percentage by mass: 40% of chromium powder, 60% of copper powder and 1-5 layers of graphene oxide, wherein the particle size is 10 microns, and the addition amount of the graphene oxide is 0.001-0.005% of the mass fraction of the chromium powder. The purity of the chromium powder is 99.9 percent, and the granularity is 1000 meshes; the purity of the copper powder is 99.9 percent, and the granularity is 200 meshes; preparing a KH-550 silane coupling agent graphene oxide solution: alcohol-water ratio 0.5: 10, keeping the KH-550 content at 0.5% by volume, standing for hydrolysis for 6h, adding graphene oxide, and ultrasonically stirring for 45 min; washing chromium powder with absolute ethyl alcohol and ultrasonically cleaning with deionized water twice, then layering by using a centrifugal machine, selecting chromium powder with smaller upper-layer particle size and uniform distribution, sieving the chromium powder with a 1000-mesh sieve, pouring the sieved chromium powder into a pickling solution of 12.0g/L for pickling for 15s, and cleaning again with deionized water after pickling; reacting the silane coupling agent graphene oxide solution prepared from chromium powder at constant temperature of 100 ℃ for 35 min; after vacuum filtration, drying the powder at 75 ℃ to prepare chromium powder @ graphene oxide core-shell structure powder; and (2) putting the powder into a hydrazine hydrate solution, keeping the temperature at 90 ℃, magnetically stirring for 15h, centrifuging to collect a product, washing the product with water and methanol for 3 times respectively, and carrying out vacuum freeze drying for 36h to reduce the graphene oxide in the chromium powder @ graphene oxide core-shell structure, thereby preparing the chromium @ graphene core-shell structure powder. Carrying out ball milling and powder mixing on chromium powder, graphene and copper powder, wherein the ball milling speed is 250r/min, the ball milling speed is 10min in positive rotation, the ball milling time is 2h, and the stopping time is 5 min; then cold press molding is carried out, the applied pressure of the cold press molding is 150MPa, the pressure maintaining time is 50s, the powder block body which is formed by the press molding is smelted in a non-consumable electric arc smelting device, and the vacuum degree is 2x10-3Pa, the maximum current of 500A and the tungsten electrode size of 12mm, and preparing the copper-chromium alloy electrical contact composite material with refined chromium.
Example 5
The composite material comprises the following components in percentage by mass: 30% of chromium powder, 70% of copper powder and 1-5 layers of graphene oxide, wherein the particle size is 10 microns, and the addition amount of the graphene oxide is 0.001-0.005% of the mass fraction of the chromium powder. The purity of the chromium powder is 99.9 percent, and the granularity is 1000 meshes; the purity of the copper powder is 99.9 percent, and the granularity is 200 meshes; preparing a KH-550 silane coupling agent graphene oxide solution: alcohol-water ratio 2: 12, keeping the KH-550 content at 0.4% by volume, standing for hydrolysis for 10h, adding graphene oxide, and ultrasonically stirring for 30 min; washing chromium powder with absolute ethyl alcohol and ultrasonically cleaning with deionized water twice, then layering by using a centrifugal machine, selecting chromium powder with smaller upper-layer particle size and uniform distribution, sieving the chromium powder with a 1000-mesh sieve, pouring the sieved chromium powder into an acid washing solution with the acid washing time of 15s for acid washing, pickling in the acid washing solution, and cleaning again with deionized water after acid washing; reacting the silane coupling agent graphene oxide solution prepared from chromium powder at a constant temperature of 90 ℃ for 55 min; after vacuum filtration, drying the powder at 75 ℃ to prepare chromium powder @ graphene oxide core-shell structure powder; and (2) putting the powder into a hydrazine hydrate solution, keeping the temperature at 85 ℃, magnetically stirring for 12h, centrifuging to collect a product, washing the product with water and methanol for 3 times respectively, and carrying out vacuum freeze drying for 40h to reduce the graphene oxide in the chromium powder @ graphene oxide core-shell structure, thereby preparing the chromium @ graphene core-shell structure powder. Carrying out ball milling and powder mixing on chromium powder, graphene and copper powder, wherein the ball milling speed is 150 r/min, the positive rotation speed is 10min, the stopping is 5min, and the ball milling time is 4 h; then cold press molding is carried out, the applied pressure of the cold press molding is 200MPa, the pressure maintaining time is 60s, the powder block body which is formed by the press molding is smelted in a non-consumable electric arc smelting device, and the vacuum degree is 2X10-3Pa, the maximum current of 400A and the tungsten electrode size of 12mm, and preparing the copper-chromium alloy electrical contact composite material with refined chromium.
Example 6
The composite material comprises the following components in percentage by mass: the chromium powder accounts for 50 percent, the copper powder accounts for 50 percent, the graphene oxide accounts for 1-5 layers, the particle size is 10 microns, and the addition amount of the graphene oxide accounts for 0.001-0.005 percent of the mass fraction of the chromium powder. The purity of the chromium powder is 99.9 percent, and the granularity is 1000 meshes; the purity of the copper powder is 99.9 percent, and the granularity is 200 meshes; preparation of KH-550 silane coupling agent oxidized stoneInk-ene solution: alcohol-water ratio of 1: 11, the KH-550 content is 0.4% by volume, standing and hydrolyzing for 6h, adding graphene oxide, and ultrasonically stirring for 60 min; washing chromium powder with absolute ethyl alcohol and ultrasonically cleaning with deionized water twice, layering by using a centrifugal machine, selecting chromium powder with a smaller upper layer grain size and uniform distribution, sieving with a 1000-mesh sieve, pouring the sieved chromium powder into a 16.0g/L pickling solution for pickling, pickling in the pickling solution with the pickling time of 8s, and cleaning with deionized water again after pickling; reacting the silane coupling agent graphene oxide solution prepared from chromium powder at constant temperature of 100 ℃ for 30 min; after vacuum filtration, drying the powder at 50 ℃ to prepare chromium powder @ graphene oxide core-shell structure powder; and (2) putting the powder into a hydrazine hydrate solution, keeping the temperature at 85 ℃, magnetically stirring for 12h, centrifuging to collect a product, washing the product with water and methanol for 3 times respectively, and carrying out vacuum freeze drying for 32h to reduce the graphene oxide in the chromium powder @ graphene oxide core-shell structure, thereby preparing the chromium @ graphene core-shell structure powder. Carrying out ball milling and powder mixing on chromium powder, graphene and copper powder, wherein the ball milling speed is 250r/min, the ball milling speed is 10min in positive rotation, the ball milling time is 2h, and the stopping time is 5 min; then cold press molding is carried out, the applied pressure of the cold press molding is 300MPa, the pressure maintaining time is 30s, the powder block body which is formed by the press molding is smelted in a non-consumable electric arc smelting device, and the vacuum degree is 2x10-3Pa, the maximum current of 300A and the size of the tungsten electrode of 12mm, and preparing the copper-chromium alloy electrical contact composite material with refined chromium.
Comparative example 1 (graphene not coated, directly added)
The composite material comprises the following components in percentage by mass: 10 percent of chromium powder, 90 percent of copper powder, 99.9 percent of chromium powder purity and 1000 meshes of granularity; the purity of the copper powder is 99.9 percent, and the granularity is 200 meshes; 1-5 layers of graphene oxide, wherein the particle size is 10 microns, and the content of graphene is 0.003%; washing chromium powder with absolute ethyl alcohol and ultrasonically cleaning with deionized water twice, then layering by using a centrifugal machine, selecting chromium powder with smaller upper-layer particle size and uniform distribution, sieving the chromium powder with a 1000-mesh sieve, pouring the sieved chromium powder into 16.0g/L acetic acid, pickling in pickling solution for 5s, and cleaning with deionized water again after pickling; directly mixing chromium powder, graphene powder and copper powder, and performing ball milling and powder mixing at the ball milling rotation speedRotating at 150 rpm for 10min, stopping for 5min, and ball milling for 4 h; then cold press molding is carried out, the applied pressure of the cold press molding is 100MPa, the pressure maintaining time is 60s, the powder block body which is formed by the press molding is smelted in a non-consumable electric arc smelting device, and the vacuum degree is 2x10-3Pa, the maximum current of 400A and the tungsten electrode size of 12mm, and preparing the copper-chromium alloy electrical contact composite material with refined chromium.
Comparative example 2 (graphene not added)
The composite material comprises the following components in percentage by mass: 10% of chromium powder and 90% of copper powder. The purity of the chromium powder is 99.9 percent, and the granularity is 1000 meshes; the purity of the copper powder is 99.9 percent, and the granularity is 200 meshes; washing chromium powder with absolute ethyl alcohol and ultrasonically cleaning with deionized water twice, then layering by using a centrifugal machine, selecting chromium powder with smaller upper-layer particle size and uniform distribution, sieving the chromium powder with a 1000-mesh sieve, pouring the sieved chromium powder into 16.0g/L acetic acid, pickling in pickling solution for 5s, and cleaning with deionized water again after pickling; carrying out ball milling and powder mixing on chromium powder and copper powder, wherein the ball milling rotation speed is 150 r/min, the positive rotation is carried out for 10min, the stopping is carried out for 5min, and the ball milling time is 4 h; then cold press molding is carried out, the applied pressure of the cold press molding is 100MPa, the pressure maintaining time is 60s, the powder block body which is formed by the press molding is smelted in a non-consumable electric arc smelting device, and the vacuum degree is 2x10-3Pa, the maximum current of 500A and the tungsten electrode size of 12mm, and preparing the copper-chromium alloy electrical contact composite material with refined chromium.
Comparative example 3 (ordinary hot pressed sintering)
The composite material comprises the following components in percentage by mass: 10% of chromium powder, 90% of copper powder and 1-5 layers of graphene oxide, wherein the particle size is 10 microns, and the addition amount of the graphene oxide is 0.001-0.005% of the mass fraction of the chromium powder. The purity of the chromium powder is 99.9 percent, and the granularity is 1000 meshes; the purity of the copper powder is 99.9 percent, and the granularity is 200 meshes; preparing a KH-550 silane coupling agent graphene oxide solution: alcohol-water ratio of 1: 11, the KH-550 content is 0.4% by volume, standing and hydrolyzing for 6h, adding graphene oxide, and ultrasonically stirring for 60 min; washing chromium powder with absolute ethyl alcohol and ultrasonically cleaning with deionized water twice, layering by using a centrifugal machine, selecting chromium powder with smaller upper-layer particle size and uniform distribution, sieving with a 1000-mesh sieve, pouring the sieved chromium powder into 16.0g/L acetic acid, pickling in a pickling solution for 5s, and removing the chromium powder after picklingWashing again with ionized water; reacting the silane coupling agent graphene oxide solution prepared from chromium powder at constant temperature of 100 ℃ for 30 min; after vacuum filtration, drying the powder at 50 ℃ to prepare chromium powder @ graphene oxide core-shell structure powder; and (2) putting the powder into a hydrazine hydrate solution, keeping the temperature at 85 ℃, magnetically stirring for 12h, centrifuging to collect a product, washing the product with water and methanol for 3 times respectively, and carrying out vacuum freeze drying for 32h to reduce the graphene oxide in the chromium powder @ graphene oxide core-shell structure, thereby preparing the chromium @ graphene core-shell structure powder. Carrying out ball milling and powder mixing on chromium powder, graphene and copper powder, wherein the ball milling speed is 250r/min, the ball milling speed is 10min in positive rotation, the ball milling time is 2h, and the stopping time is 5 min; then carrying out cold press molding; then carrying out vacuum hot-pressing sintering under the pressure of 20MPa, the dwell time of 180s and the vacuum degree of 2X10-1Pa, the maximum current of 400A and the tungsten electrode size of 12mm, and preparing the hot-pressed sintered copper-chromium alloy electrical contact composite material.
Comparative example 4 (graphene not coated, directly added) vs example comparative graphene coated
The composite material comprises the following components in percentage by mass: 20 percent of chromium powder, 80 percent of copper powder, 99.9 percent of chromium powder with the purity and 1000 meshes of granularity; the purity of the copper powder is 99.9 percent, and the granularity is 200 meshes; 1-5 layers of graphene oxide, wherein the particle size is 10 microns, and the content of graphene is 0.003%; washing chromium powder with absolute ethyl alcohol and ultrasonically cleaning with deionized water twice, then layering by using a centrifugal machine, selecting chromium powder with smaller upper-layer particle size and uniform distribution, sieving the chromium powder with a 1000-mesh sieve, pouring the sieved chromium powder into 16.0g/L acetic acid, pickling in pickling solution for 5s, and cleaning with deionized water again after pickling; directly mixing chromium powder, graphene powder and copper powder, and performing ball milling and powder mixing, wherein the ball milling rotation speed is 150 revolutions per minute, the positive rotation is performed for 10min, the stopping is performed for 5min, and the ball milling time is 4 h; and then carrying out cold press molding, wherein the applied pressure of the cold press molding is 100MPa, the pressure maintaining time is 60s, and vacuum sintering is carried out after the cold press molding to prepare the chromium refined copper-chromium alloy electrical contact composite material.
TABLE 1 comparison of copper-chromium alloy Properties
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (7)
1. The chromium @ graphene reinforced copper-based composite material is characterized in that: preparing chromium powder @ graphene core-shell structure powder by adopting a chemical synthesis method; mixing chromium powder @ graphene core-shell structure powder and copper powder, carrying out cold press molding, and preparing by adopting an arc melting method under the protection of inert gas; the composite material comprises the following components in percentage by mass: 10-50% of chromium powder and 90-50% of copper powder, wherein the addition amount of the graphene oxide is 0.001-0.005% of the mass fraction of the chromium powder.
2. The chromium @ graphene reinforced copper-based composite material as claimed in claim 1, wherein the purity of chromium powder is 99.9%, and the particle size is 1000 meshes; the purity of the copper powder is 99.9 percent, and the granularity is 200 meshes; 1-5 layers of graphene oxide, and the particle size is 5-20 microns.
3. The preparation method of the chromium @ graphene reinforced copper-based composite material as claimed in claim 1, is characterized by comprising the following steps:
(1) preparing a KH-550 silane coupling agent graphene oxide solution: the alcohol-water ratio is 0.5-5: 5-15%, wherein the volume fraction content of KH-550 is 0.2-1.0%, standing and hydrolyzing for 4-10 h, and adding graphene oxide and ultrasonically stirring for 30-60 min;
(2) chromium powder pretreatment: washing chromium powder with absolute ethyl alcohol and ultrasonically cleaning with deionized water twice, then layering by using a centrifugal machine, selecting chromium powder with smaller upper-layer particle size and uniform distribution, sieving by using a 1000-mesh sieve, pouring the sieved chromium powder into a pickling solution for pickling, and cleaning with deionized water again after pickling;
(3) synthesizing a chromium powder @ graphene oxide core-shell structure: pouring chromium powder into the silane coupling agent solution prepared in the step (1), and reacting at constant temperature of 40-100 ℃ for 30-60 min; after vacuum filtration, drying the powder at 50-100 ℃ to prepare chromium powder @ graphene oxide core-shell structure powder;
(4) reducing a chromium powder @ graphene oxide core-shell structure: putting the powder obtained in the step (3) into a hydrazine hydrate solution, keeping the temperature at 85-100 ℃, magnetically stirring for 10-15 h, then centrifugally collecting a product, washing for 3 times with water and methanol respectively, and carrying out vacuum freeze drying for 24-48 h to reduce the graphene oxide in the chromium powder @ graphene oxide core-shell structure, thereby preparing the chromium powder @ graphene core-shell structure powder;
(5) ball-milling and mixing the chromium powder @ graphene core-shell structure powder prepared in the step (4) and copper powder;
(6) carrying out cold press molding after ball milling and powder mixing;
(7) and performing non-consumable arc melting on the formed powder block, and performing plastic processing forming to prepare the chromium @ graphene reinforced copper-based composite material.
4. The method according to claim 3, wherein the pickling solution is acetic acid of 6.0 to 16.0g/L, and the pickling time is 5 to 20 seconds.
5. The method as claimed in claim 3, wherein the ball mill is pumped by a mechanical pump, evacuated and filled with argon for protection, the rotation speed is 150-.
6. The preparation method according to claim 3, wherein the cold press molding is performed under an applied pressure of 100 to 300MPa and a dwell time of 15 to 60 seconds.
7. The preparation method according to claim 3, wherein the specific parameters of the arc melting are as follows: the vacuum degree is 0.01Pa, the current is 100-500A, and the size of the tungsten electrode is 12 mm.
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| CN104637566A (en) * | 2015-02-16 | 2015-05-20 | 中国科学院宁波材料技术与工程研究所 | Metal/graphene composite material and preparation method as well as application thereof |
| CN108031837A (en) * | 2017-11-23 | 2018-05-15 | 西安理工大学 | A kind of method for preparing chromium plating graphene/copper composite powder |
| CN108034930A (en) * | 2017-11-22 | 2018-05-15 | 华中科技大学 | A kind of preparation method of graphene/metallic composite and three-dimensional grapheme |
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| CN104451227A (en) * | 2014-12-10 | 2015-03-25 | 济南大学 | Preparation method of copper-plated graphene reinforced metal-based composite |
| CN104637566A (en) * | 2015-02-16 | 2015-05-20 | 中国科学院宁波材料技术与工程研究所 | Metal/graphene composite material and preparation method as well as application thereof |
| CN108034930A (en) * | 2017-11-22 | 2018-05-15 | 华中科技大学 | A kind of preparation method of graphene/metallic composite and three-dimensional grapheme |
| CN108031837A (en) * | 2017-11-23 | 2018-05-15 | 西安理工大学 | A kind of method for preparing chromium plating graphene/copper composite powder |
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