CN111822308A - CeO (CeO)2Modified nano Ag whisker doped graphene film and preparation method thereof - Google Patents
CeO (CeO)2Modified nano Ag whisker doped graphene film and preparation method thereof Download PDFInfo
- Publication number
- CN111822308A CN111822308A CN202010731300.2A CN202010731300A CN111822308A CN 111822308 A CN111822308 A CN 111822308A CN 202010731300 A CN202010731300 A CN 202010731300A CN 111822308 A CN111822308 A CN 111822308A
- Authority
- CN
- China
- Prior art keywords
- ceo
- whisker
- film
- nano
- modified nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/002—Pretreatement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0209—Multistage baking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
- B05D3/0272—After-treatment with ovens
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
- C23C18/127—Preformed particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/40—Metallic substrate based on other transition elements
- B05D2202/45—Metallic substrate based on other transition elements based on Cu
Abstract
The invention discloses CeO2The preparation method of the modified nano Ag whisker doped graphene film comprises the following steps: step (1), pretreating a substrate; step (2), preparing cerous nitrate gel; step (3), preparing gel suspension containing cerous nitrate and nano Ag whiskers; step (4), CeO2Preparing a modified nano Ag whisker porous film; step (5), CeO2Reducing and preparing the modified nano Ag whisker doped graphene oxide composite film; and (6) heating the graphene film. The invention also discloses CeO obtained by the preparation method2The modified nano Ag whisker is doped with a graphene film. CeO is introduced to the surfaces of a carbon brush of a high-speed train and a copper alloy friction disc of a motor rotor2The rare earth oxide modified Ag whisker doped graphene film has the advantages that the excellent electrical conductivity and thermal conductivity of the friction disc are maintained, and the current-carrying wear resistance and arc ablation resistance of the friction disc are improved.
Description
Technical Field
The invention relates to CeO2A modified nano Ag whisker doped graphene film and a preparation method thereof belong to the technical field of materials.
Background
At present, the high speed of the train becomes the mainstream of the railway industry, and the high-power electric traction system becomes the prime power of the high-speed train. The industry related to high-speed rails is rapidly and increasingly developed, and the friction disc parts of the rotor of the traction motor of the high-speed train, which are key parts of the friction disc parts, are gradually made into a home. In a traction transmission system, the carbon brushes of a high-speed train and the friction discs of a motor rotor are mainly made of copper alloy with good conductivity and wear resistance. However, when the carbon brushes and the motor rotor friction discs of the high-speed train work under a current-carrying working condition for a long time, serious heating and arc ablation phenomena can be generated, and even the friction discs can reduce the wear resistance due to overheating, so that the safety and the stability of the whole train operation are endangered. Therefore, the key problems of arc erosion resistance, heat resistance and heat conductivity are solved while the carbon brush of the high-speed train in the traction motor and the friction disc element of the motor rotor have good electrical conductivity and wear resistance.
In recent years, with the rapid development of cooling technology, coating a graphene film with excellent electric conduction and heat conduction performance on the surface of a copper alloy of a carbon brush of a high-speed train and a friction disc of a motor rotor becomes a better method for solving the problems of electric conduction and arc ablation resistance of the carbon brush of the high-speed train and the friction disc of the motor rotor. Graphene is a typical two-dimensional crystal carbon material, the crystal structure of which is a honeycomb net-shaped hexagonal structure formed by carbon atoms layer by layer, and the graphene is the most ideal two-dimensional material at present. The graphene has high elastic modulus and electrical conductivity and extremely high thermal conductivity (about 5000 W.m)-1·K-1). In the aspect of research on the electric and thermal conductivity of the graphene metal composite material, the excellent plane electric and thermal conductivity of graphene can be effectively exerted through the Ag-doped nano particles, the crystal whiskers and the film layer with good electric and thermal conductivity, and the electric and thermal conductivity of the metal film material is improved. However, because the stability of the microstructure of the Ag whisker and the film layer at high temperature is poor, the hardness and the wear resistance are rapidly reduced, and the arc ablation resistance is poor under the working condition of carrying current. Therefore, the existing Ag crystal whiskers and film-doped graphene are not suitable for being applied to the friction disc of the motor rotor of the high-speed train. Therefore, the excellent electric conduction, heat conduction, wear resistance and high temperature resistance of graphene are exerted to the greatest extent, and the surface graphene composite film meeting the service working condition requirements of the high-speed train carbon brush and the motor rotor friction disc of the high-speed train traction motor is prepared.
Disclosure of Invention
The invention aims to solve the technical problem that the CeO on the surface of the copper alloy can improve the electrical conductivity and the wear resistance of a carbon brush of a high-speed train and a friction disc of a motor rotor and has good thermal conductivity2Modified nano Ag whisker dopingA hybrid graphene film and a preparation method thereof;
further, the invention provides a method for improving the conductivity of the graphene film by doping Ag whiskers; meanwhile, CeO with arc ablation resistance and high temperature resistance is introduced to the surface of the Ag whisker2CeO for effectively protecting nano Ag crystal whisker from high-temperature oxidation2A modified nano Ag whisker doped graphene film and a preparation method thereof;
furthermore, the invention provides a method for preventing oxygen atoms from diffusing into the Ag whiskers, reducing the damage of high-temperature oxidation to the Ag whisker formation and simultaneously providing CeO2The CeO has no obvious influence on the conductivity of the nano Ag crystal whisker and effectively prevents the problem of conductivity reduction caused by the combination of O atoms and the Ag crystal whisker2A modified nano Ag whisker doped graphene film and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
CeO (CeO)2The preparation method of the modified nano Ag whisker doped graphene film comprises the following steps:
the method comprises the following steps of (1) pretreating a high-speed train carbon brush and a motor rotor friction disc by using a copper alloy as a matrix, and then performing surface pretreatment, wherein the surface pretreatment comprises oxide film removal, metallographic phase grinding, polishing and cleaning; drying the surface for later use after cleaning;
step (2), weighing 1-5 parts by weight of cerous nitrate, adding the cerous nitrate into 100-120 parts by weight of deionized water to obtain a solution, adding a citric acid complexing agent and a polyethylene glycol dispersing agent, wherein the molar ratio of citric acid to Ce ions is (1-1.5): 1, and the molar ratio of polyethylene glycol to Ce ions is (1-2): 1, stirring for dissolving, and fully stirring and mixing in a water bath at 80-100 ℃ to form gel;
step (3), dipping 20-30 parts by weight of nano Ag whiskers into the gel, and stirring for 20-40 minutes to disperse the nano Ag whiskers into the gel obtained in the step (2) in a suspension form to obtain a gel suspension containing cerous nitrate, the nano Ag whiskers, citric acid and polyethylene glycol;
step (4) of immersing the substrate in the gel suspension obtained in step (3) 1Drying at 150-200 ℃ for 5-25 minutes, and then treating at 500-600 ℃ for 2-3 hours to obtain CeO on the surface of the matrix2Modifying the nano Ag whisker porous film;
step (5), weighing 60-120 parts by weight of graphene oxide, adding the graphene oxide into 500 parts by weight of evaporable solvent, uniformly stirring and ultrasonically dispersing for 15-60 minutes to obtain graphene oxide dispersion liquid, coating the graphene oxide dispersion liquid on the porous membrane prepared in the step (4), slowly evaporating the evaporable solvent in the graphene oxide dispersion liquid, and then, evaporating CeO2Transferring the modified nano Ag whisker doped graphene oxide composite film into high-temperature calcining equipment, treating at-800-900 ℃ for 90-120 minutes, and carrying out thermal reduction in a high-temperature hydrogen atmosphere to obtain a graphene film, namely the CeO2The modified nano Ag whisker is doped with a graphene film;
and (6) heating the graphene film: and (3) placing the film in high-temperature calcining equipment, heating the film by a program, cooling the film to room temperature along with a furnace, and taking out the film to obtain the high-temperature-resistant high-temperature-.
The cleaning comprises ultrasonic cleaning, the cleaning time is 20-40 min, and the cleaning medium is acetone.
The coating thickness of the graphene oxide dispersion liquid is 100-500 mu m.
The evaporable solvent comprises deionized water or absolute ethanol.
The high-temperature calcining equipment comprises a tubular heating furnace.
The method for removing the oxide film comprises a method of using a grinder or cutting; the metallographic polishing comprises polishing by using multiple metallographic abrasive paper; the polishing agent used in the polishing process is nano diamond paste.
The temperature programming method comprises the following steps: heating at 100-150 ℃ for 2-3 hours, then heating at 200-300 ℃ for 2-3 hours, and then heating at 300-400 ℃ for 2-3 hours.
Adopting the CeO of the invention2CeO obtained by preparation method of modified nano Ag whisker doped graphene film2The modified nano Ag whisker is doped with a graphene film.
In step (4) of the present inventionThe gel mainly containing cerous nitrate and nano Ag whiskers is dried to form a film formed by mixing cerous nitrate, nano Ag whiskers and organic matters, the cerous nitrate and the organic matters are evaporated and decomposed in the heating process to form a film with a porous structure, a channel is provided for the penetration and diffusion of the graphene dispersion liquid, and the preparation efficiency is improved. At the same time, CeO attached to the surface of the nano Ag whisker2The nano particles can effectively prevent oxygen molecules in the air from entering the interior of the nano Ag crystal whisker at high temperature, so that the oxidation resistance of the nano Ag crystal whisker is improved.
In the invention, graphene oxide is reduced in the step (5), the reduced graphene oxide is graphene, and after the conventional graphene oxide is subjected to thermal deoxygenation treatment at a high temperature of 800 ℃, the carbon content can be increased to about 90%, but the conductivity is still not high, because the defects on the graphene sheet are not repaired at a high temperature. The final repairing effect can be improved by carrying out chemical reduction and then carrying out high-temperature thermal reduction; the repair effect after heat treatment can also be increased by performing the treatment under a hydrogen atmosphere at a high temperature.
The multi-stage heat treatment adopted in the step (6) of the invention has the effects of improving the diffusion and transmission of the graphene to the surface of the matrix, reducing a small amount of residual water molecules and organic molecules in the film and improving the purity and density of the film.
In the invention with CeO2Modifying nano Ag crystal whisker and graphene oxide as precursor, and adding nano CeO2The modified nano Ag crystal whisker and the graphene form a film material by a self-assembly method, so that the excellent electric conduction, heat conduction, wear resistance and high temperature resistance of the graphene can be exerted to the greatest extent, and the surface graphene composite film meeting the service working condition requirements of a high-speed train carbon brush and a motor rotor friction disc of a high-speed train traction motor is prepared. Thus CeO2The modified nano Ag whisker doped graphene film can obviously improve the electric and thermal conductivity, high-temperature wear resistance and ablation resistance of the surface of the copper alloy for the motor rotor friction disc for the high-speed train.
CeO of the invention2The modified nano Ag whisker doped graphene film is prepared by taking the Ag whisker as a copper alloy for a motor rotor friction disc as a suitable base material, and grinding and cleaning the copper alloySkeleton of CeO2The porous membrane is obtained by modifying the surface of the nano Ag whisker, and the porous membrane is well combined with a matrix due to good wettability between Cu and Ag. Then obtaining CeO by infiltrating graphene dispersion liquid2The modified nano Ag whisker doped graphene film is formed by CeO2In the presence of the graphene composite film, the graphene composite film has better ablation resistance and high temperature resistance.
The invention has the following beneficial effects: the invention provides a concept of nano Ag whisker doping and modification design on the basis of a graphene film, utilizes nano Ag whiskers to cause the electric and thermal conductivity of the graphene film to be increased, utilizes nano Ag whiskers to form a film framework to support the graphene film, and simultaneously utilizes a rare earth modification technology to add CeO2And the nano Ag whisker is attached to the surface of the nano Ag whisker, so that the high-temperature ablation resistance and frictional wear resistance of the nano Ag whisker doped graphene film layer are improved, and the conductivity of the nano Ag whisker is well kept, so that the nano Ag whisker is suitable for improving the service performance and the service life of a high-speed train carbon brush and a motor rotor friction disc under working conditions such as copper alloy current-carrying friction.
CeO is introduced to the surfaces of a carbon brush of a high-speed train and a copper alloy friction disc of a motor rotor2The rare earth oxide modified Ag whisker doped graphene film has the advantages that excellent electrical conductivity and thermal conductivity are maintained, and meanwhile, the current-carrying wear resistance and arc ablation resistance of the graphene film on the surface of the copper alloy are improved, so that the graphene film is suitable for high-temperature friction conditions and can meet the requirements of high electrical conductivity, current-carrying friction and other working conditions of high-speed train carbon brushes and motor rotor friction discs under various complex working conditions.
Drawings
FIG. 1 shows CeO prepared in example 12SEM pictures of the surface of the modified nano Ag whisker porous membrane;
FIG. 2 shows CeO prepared in example 12SEM (scanning electron microscope) picture of the surface of the modified nano Ag whisker doped graphene film;
FIG. 3 shows CeO prepared in example 32SEM (scanning electron microscope) picture and main element line scanning picture of the cross section appearance of the modified nano Ag whisker doped graphene film.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. The specific embodiments described herein are merely illustrative of the invention and are not intended to be limiting.
Example 1:
CeO (CeO)2The preparation method of the modified nano Ag whisker doped graphene film comprises the following steps:
the method comprises the following steps of (1) pretreating a high-speed train carbon brush and a motor rotor friction disc by using a copper alloy as a matrix, and then performing surface pretreatment, wherein the surface pretreatment comprises oxide film removal, metallographic phase grinding, polishing and cleaning; drying the surface for later use after cleaning; the cleaning is ultrasonic cleaning, the cleaning time is 20min, and the cleaning medium is acetone; the method for removing the oxidation film is a method adopting a grinding machine; the metallographic polishing is performed by using multiple metallographic abrasive paper; the polishing agent used in the polishing process is a nano diamond paste;
weighing 1 part by weight of cerous nitrate, adding the cerous nitrate into 100 parts by weight of deionized water to obtain a solution, adding a citric acid complexing agent and a polyethylene glycol dispersing agent, wherein the molar ratio of citric acid to Ce ions is 1:1, and the molar ratio of polyethylene glycol to Ce ions is 1:1, stirring for dissolving, and fully stirring and mixing in a water bath at 90 ℃ to obtain gel;
step (3), dipping 20 parts by weight of nano Ag whiskers into the gel, and stirring for 30 minutes to disperse the nano Ag whiskers into the gel obtained in the step (2) in a suspension form to obtain a gel suspension containing cerous nitrate, the nano Ag whiskers, citric acid and polyethylene glycol;
step (4), soaking the substrate in the gel suspension obtained in the step (3) for 20 minutes, drying at 150 ℃, and then treating at 500 ℃ for 2 hours to obtain CeO on the surface of the substrate2Modifying the nano Ag whisker porous film;
step (5), weighing 60 parts by weight of graphene oxide, adding the graphene oxide into 300 parts by weight of deionized water, uniformly stirring, and ultrasonically dispersing for 15 minutes to obtain a graphene oxide dispersion liquidCoating the graphene oxide dispersion liquid on the porous membrane prepared in the step (4) to a thickness of 100 microns, slowly evaporating deionized water in the dispersion liquid, and then, carrying out CeO (CeO) evaporation2Transferring the modified nano Ag whisker doped graphene oxide composite film into a tubular heating furnace, treating at 800 ℃ for 90 minutes, and carrying out thermal reduction in a high-temperature hydrogen atmosphere to obtain a graphene film, namely the CeO2The modified nano Ag whisker is doped with a graphene film;
and (6) placing the graphene film in a tubular heating furnace, heating for 2 hours at 100 ℃, heating for 2 hours at 200 ℃, heating for 2 hours at 300 ℃, cooling to room temperature along with the furnace, and taking out the graphene film.
Example 2:
CeO (CeO)2The preparation method of the modified nano Ag whisker doped graphene film comprises the following steps:
the method comprises the following steps of (1) pretreating a high-speed train carbon brush and a motor rotor friction disc by using a copper alloy as a matrix, and then performing surface pretreatment, wherein the surface pretreatment comprises oxide film removal, metallographic phase grinding, polishing and cleaning; drying the surface for later use after cleaning; the cleaning is ultrasonic cleaning, the cleaning time is 40min, and the cleaning medium is acetone; the method for removing the oxide film is a cutting method; the metallographic polishing is performed by using multiple metallographic abrasive paper; the polishing agent used in the polishing process is a nano diamond paste;
step (2), weighing 5 parts by weight of cerous nitrate, adding the cerous nitrate into 120 parts by weight of deionized water to obtain a solution, adding a citric acid complexing agent and a polyethylene glycol dispersing agent, wherein the molar ratio of citric acid to Ce ions is 1:1, and the molar ratio of polyethylene glycol to Ce ions is 2:1, stirring for dissolving, and fully stirring and mixing in a water bath at 90 ℃ to obtain gel;
step (3), dipping 20 parts by weight of nano Ag whiskers into the gel, and stirring for 30 minutes to disperse the nano Ag whiskers into the gel obtained in the step (2) in a suspension form to obtain a gel suspension containing cerous nitrate, the nano Ag whiskers, citric acid and polyethylene glycol;
step (4), dipping the matrix in the gel suspension obtained in the step (3)Drying in the turbid liquid at 150 deg.C for 20min, and treating at 500 deg.C for 2 hr to obtain CeO on the surface of the substrate2Modifying the nano Ag whisker porous film;
step (5), weighing 80 parts by weight of graphene oxide, adding the graphene oxide into 300 parts by weight of absolute ethyl alcohol, uniformly stirring and ultrasonically dispersing for 15 minutes to obtain a graphene oxide dispersion liquid, coating the graphene oxide dispersion liquid on the porous membrane prepared in the step (4) to a thickness of 120 mu m, slowly evaporating the absolute ethyl alcohol in the dispersion liquid, and then, adding CeO2Transferring the modified nano Ag whisker doped graphene oxide composite film into high-temperature calcining equipment, treating at 800 ℃ for 90 minutes, and carrying out thermal reduction in a high-temperature hydrogen atmosphere to obtain a graphene film, namely the CeO2The modified nano Ag whisker is doped with a graphene film; the high-temperature calcining equipment is a tubular heating furnace;
and (6) placing the graphene film in a tubular heating furnace, heating for 2 hours at 100 ℃, heating for 2 hours at 200 ℃, heating for 2 hours at 300 ℃, cooling to room temperature along with the furnace, and taking out the graphene film.
Example 3:
CeO (CeO)2The preparation method of the modified nano Ag whisker doped graphene film comprises the following steps:
the method comprises the following steps of (1) pretreating a high-speed train carbon brush and a motor rotor friction disc by using a copper alloy as a matrix, and then performing surface pretreatment, wherein the surface pretreatment comprises oxide film removal, metallographic phase grinding, polishing and cleaning; drying the surface for later use after cleaning;
weighing 1 part by weight of cerous nitrate, adding the cerous nitrate into 120 parts by weight of deionized water to obtain a solution, adding a citric acid complexing agent and a polyethylene glycol dispersing agent, wherein the molar ratio of citric acid to Ce ions is 1:1, and the molar ratio of polyethylene glycol to Ce ions is 2:1, stirring for dissolving, and fully stirring and mixing in a water bath at 90 ℃ to obtain gel;
step (3), dipping 20 parts by weight of nano Ag whiskers into the gel, and stirring for 30 minutes to disperse the nano Ag whiskers into the gel obtained in the step (2) in a suspension form to obtain a gel suspension containing cerous nitrate, the nano Ag whiskers, citric acid and polyethylene glycol;
step (4), soaking the substrate in the gel suspension obtained in the step (3) for 20 minutes, drying at 150 ℃, and then treating at 500 ℃ for 2 hours to obtain CeO on the surface of the substrate2Modifying the nano Ag whisker porous film;
step (5), weighing 120 parts by weight of graphene oxide, adding into 300 parts by weight of deionized water or absolute ethyl alcohol, uniformly stirring and ultrasonically dispersing for 15 minutes to obtain graphene oxide deionized water or absolute ethyl alcohol dispersion liquid, coating the graphene oxide deionized water or absolute ethyl alcohol dispersion liquid on the porous membrane prepared in the step (4) with the thickness of 500 mu m, slowly evaporating the deionized water or absolute ethyl alcohol in the dispersion liquid, and then, adding CeO2Transferring the modified nano Ag whisker doped graphene oxide composite film into high-temperature calcining equipment, treating at 800 ℃ for 90 minutes, and carrying out thermal reduction in a high-temperature hydrogen atmosphere to obtain a graphene film, namely the CeO2The modified nano Ag whisker is doped with a graphene film; the high-temperature calcining equipment is a tubular heating furnace;
and (6) placing the graphene film in a tubular heating furnace, heating for 2 hours at 100 ℃, heating for 2 hours at 200 ℃, heating for 2 hours at 300 ℃, cooling to room temperature along with the furnace, and taking out the graphene film.
Example 4:
CeO (CeO)2The preparation method of the modified nano Ag whisker doped graphene film comprises the following steps:
the method comprises the following steps of (1) pretreating a high-speed train carbon brush and a motor rotor friction disc by using a copper alloy as a matrix, and then performing surface pretreatment, wherein the surface pretreatment comprises oxide film removal, metallographic phase grinding, polishing and cleaning; drying the surface for later use after cleaning;
weighing 1 part by weight of cerous nitrate, adding the cerous nitrate into 120 parts by weight of deionized water to obtain a solution, adding a citric acid complexing agent and a polyethylene glycol dispersing agent, wherein the molar ratio of citric acid to Ce ions is 1:1, and the molar ratio of polyethylene glycol to Ce ions is 2:1, stirring for dissolving, and fully stirring and mixing in a water bath at 90 ℃ to obtain gel;
step (3), soaking 30 parts by weight of nano Ag whiskers in the gel, and stirring for 30 minutes to disperse the nano Ag whiskers in the gel obtained in the step (2) in a suspension form to obtain a gel suspension containing cerous nitrate, the nano Ag whiskers, citric acid and polyethylene glycol;
step (4), soaking the substrate in the gel suspension obtained in the step (3) for 20 minutes, drying at 150 ℃, and then treating at 500 ℃ for 2 hours to obtain CeO on the surface of the substrate2Modifying the nano Ag whisker porous film;
step (5), weighing 120 parts by weight of graphene oxide, adding into 300 parts by weight of deionized water or absolute ethyl alcohol, uniformly stirring and ultrasonically dispersing for 15 minutes to obtain graphene oxide deionized water or absolute ethyl alcohol dispersion liquid, coating the graphene oxide deionized water or absolute ethyl alcohol dispersion liquid on the porous membrane prepared in the step (4) with the thickness of 500 mu m, slowly evaporating the deionized water or absolute ethyl alcohol in the dispersion liquid, and then, adding CeO2Transferring the modified nano Ag whisker doped graphene oxide composite film into high-temperature calcining equipment, treating at 800 ℃ for 90 minutes, and carrying out thermal reduction in a high-temperature hydrogen atmosphere to obtain a graphene film, namely the CeO2The modified nano Ag whisker is doped with a graphene film;
and (6) placing the graphene film in a tubular heating furnace, heating for 2 hours at 100 ℃, heating for 2 hours at 200 ℃, heating for 2 hours at 300 ℃, cooling to room temperature along with the furnace, and taking out the graphene film.
CeO of examples 1 to 42The electric conductivity and the thermal conductivity of the modified nano Ag whisker doped graphene film and the friction coefficient under the conditions of 100N load, 50m/s sliding speed, 150A load current and 300 ℃ are shown in Table 1, wherein a friction pair working in current-carrying friction is a copper alloy friction disc-carbon brush.
Table 1 table of conductivity, thermal conductivity, and coefficient of friction of graphene film
Table 1 shows the CeO values of examples 1 to 42The modified nano Ag whisker doped graphene film has the advantages that the electric conductivity and the heat conductivity coefficient and the friction coefficient data under the conditions of 100N load, 50m/s sliding speed, 150A load current and 300 ℃ temperature are shown, the copper alloy matrix in the table 1 is a comparative example, is a high-speed train motor rotor friction disc in the prior art and is also a matrix in the invention.
Notably, CeO2The electric conductivity, the heat conductivity coefficient and the friction coefficient of the modified nano Ag whisker doped graphene film are related to the proportion of each component and the thickness of a film layer.
Example 5:
this example differs from example 1 only in that: in the step (2), the molar ratio of citric acid to Ce ions is 1.5: 1; in the step (4), the substrate is immersed in the gel suspension obtained in the step (3) for 15 minutes, dried at 200 ℃, and then treated at 600 ℃ for 3 hours; in the step (5), weighing 100 parts by weight of graphene oxide, adding the graphene oxide into 500 parts by weight of evaporable solvent, uniformly stirring and ultrasonically dispersing for 60 minutes to obtain graphene oxide dispersion liquid, coating the graphene oxide dispersion liquid on the porous membrane prepared in the step (4), slowly evaporating the evaporable solvent in the dispersion liquid, and then, evaporating CeO2Transferring the modified nano Ag whisker doped graphene oxide composite film into high-temperature calcination equipment, and treating for 120 minutes at 900 ℃; in the step (6), the method for temperature programming comprises the following steps: after heating at 150 ℃ for 3 hours, further heating at 300 ℃ for 3 hours, and further heating at 400 ℃ for 3 hours.
Example 6:
this example differs from example 5 only in that:
in step (4), the matrix is immersed in the gel suspension obtained in step (3) for 25 minutes.
Example 7:
CeO prepared by the method of examples 1 to 72The modified nano Ag whisker is doped with a graphene film.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. CeO (CeO)2The preparation method of the modified nano Ag whisker doped graphene film is characterized by comprising the following steps: the method comprises the following steps:
step (1), pretreatment of a matrix: taking a friction disc as a substrate and pretreating the friction disc;
step (2), preparation of cerous nitrate gel: weighing 1-5 parts by weight of cerous nitrate, adding the cerous nitrate into 100-120 parts by weight of deionized water to obtain a solution, adding a citric acid complexing agent and a polyethylene glycol dispersing agent, wherein the molar ratio of citric acid to Ce ions is (1-1.5): 1, and the molar ratio of polyethylene glycol to Ce ions is (1-2): 1, stirring and dissolving, and fully stirring and mixing in a water bath at the temperature of 80-100 ℃ to form gel;
step (3), preparing gel suspension containing cerous nitrate and nano Ag whiskers: dipping 20-30 parts by weight of nano Ag whiskers in the gel, and stirring for 20-40 minutes to disperse the nano Ag whiskers in the gel obtained in the step (2) in a suspension form to obtain a gel suspension containing cerous nitrate, the nano Ag whiskers, citric acid and polyethylene glycol;
step (4), CeO2Preparing a modified nano Ag whisker porous film: soaking a substrate in the gel suspension obtained in the step (3) for 15-25 minutes, drying at 150-200 ℃, and then treating at 500-600 ℃ for 2-3 hours to obtain CeO on the surface of the substrate2Modifying the nano Ag whisker porous film;
step (5), CeO2The modified nano Ag whisker doped graphene oxide composite film is prepared by reduction: weighing 60-120 parts by weight of graphene oxide, adding the graphene oxide into 300-500 parts by weight of evaporable solvent, uniformly stirring and ultrasonically dispersing for 15-60 minutes to obtain the graphene oxideCoating the graphene oxide dispersion on the porous membrane prepared in the step (4), slowly evaporating the evaporable solvent in the dispersion, and then, carrying out CeO2Transferring the modified nano Ag whisker doped graphene oxide composite film into high-temperature calcining equipment, treating at 800-900 ℃ for 90-120 minutes, and carrying out thermal reduction in a high-temperature hydrogen atmosphere to obtain a graphene film, namely the CeO2The modified nano Ag whisker is doped with a graphene film;
and (6) heating the graphene film: and (3) placing the film in high-temperature calcining equipment, heating the film by a program, cooling the film to room temperature along with a furnace, and taking out the film to obtain the high-temperature-resistant high-temperature-.
2. CeO according to claim 12The preparation method of the modified nano Ag whisker doped graphene film is characterized by comprising the following steps: the friction disc comprises a motor rotor copper alloy friction disc for a high-speed train.
3. CeO according to claim 12The preparation method of the modified nano Ag whisker doped graphene film is characterized by comprising the following steps: the pretreatment method comprises surface pretreatment, wherein the surface pretreatment comprises oxide film removal, metallographic phase grinding, polishing and cleaning; and drying the surface for later use after cleaning.
4. CeO according to claim 32The preparation method of the modified nano Ag whisker doped graphene film is characterized by comprising the following steps: the cleaning comprises ultrasonic cleaning, the cleaning time is 20-40 min, and the cleaning medium is acetone.
5. CeO according to claim 12The preparation method of the modified nano Ag whisker doped graphene film is characterized by comprising the following steps: the coating thickness of the graphene oxide dispersion liquid is 100-500 mu m.
6. CeO according to claim 12The preparation method of the modified nano Ag whisker doped graphene film is characterized by comprising the following steps: the can steamThe solvent comprises deionized water or absolute ethyl alcohol.
7. CeO according to claim 12The preparation method of the modified nano Ag whisker doped graphene film is characterized by comprising the following steps: the high-temperature calcining equipment comprises a tubular heating furnace.
8. CeO according to claim 32The preparation method of the modified nano Ag whisker doped graphene film is characterized by comprising the following steps: the method for removing the oxide film comprises a method of using a grinder or cutting; the metallographic polishing comprises polishing by using multiple metallographic abrasive paper; the polishing agent used in the polishing process is nano diamond paste.
9. CeO according to claim 12The preparation method of the modified nano Ag whisker doped graphene film is characterized by comprising the following steps: the temperature programming method comprises the following steps: heating at 100-150 ℃ for 2-3 hours, then heating at 200-300 ℃ for 2-3 hours, and then heating at 300-400 ℃ for 2-3 hours.
10. Use of a CeO according to any one of claims 1 to 92CeO obtained by preparation method of modified nano Ag whisker doped graphene film2The modified nano Ag whisker is doped with a graphene film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010731300.2A CN111822308B (en) | 2020-07-27 | 2020-07-27 | CeO (CeO)2Modified nano Ag whisker doped graphene film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010731300.2A CN111822308B (en) | 2020-07-27 | 2020-07-27 | CeO (CeO)2Modified nano Ag whisker doped graphene film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111822308A true CN111822308A (en) | 2020-10-27 |
| CN111822308B CN111822308B (en) | 2021-02-26 |
Family
ID=73528418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010731300.2A Active CN111822308B (en) | 2020-07-27 | 2020-07-27 | CeO (CeO)2Modified nano Ag whisker doped graphene film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111822308B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102176336A (en) * | 2010-12-30 | 2011-09-07 | 温州宏丰电工合金股份有限公司 | Preparation method of silver-based oxide electrical contact material with filamentary structure |
| CN104030275A (en) * | 2014-05-30 | 2014-09-10 | 上海应用技术学院 | Preparation method of reduction graphene oxide heat-conducting film |
| CN110844901A (en) * | 2019-11-20 | 2020-02-28 | 南京信息工程大学 | Porous graphene/silver composite membrane for friction nano generator and preparation method thereof |
| CN110876386A (en) * | 2019-11-20 | 2020-03-13 | 厦门稀土材料研究所 | Rare earth oxide and nano-silver synergistic antibacterial agent and preparation method thereof |
-
2020
- 2020-07-27 CN CN202010731300.2A patent/CN111822308B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102176336A (en) * | 2010-12-30 | 2011-09-07 | 温州宏丰电工合金股份有限公司 | Preparation method of silver-based oxide electrical contact material with filamentary structure |
| CN104030275A (en) * | 2014-05-30 | 2014-09-10 | 上海应用技术学院 | Preparation method of reduction graphene oxide heat-conducting film |
| CN110844901A (en) * | 2019-11-20 | 2020-02-28 | 南京信息工程大学 | Porous graphene/silver composite membrane for friction nano generator and preparation method thereof |
| CN110876386A (en) * | 2019-11-20 | 2020-03-13 | 厦门稀土材料研究所 | Rare earth oxide and nano-silver synergistic antibacterial agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111822308B (en) | 2021-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20150064463A1 (en) | Graphene fiber and method of manufacturing the same | |
| CN110610787A (en) | Heavy rare earth grain boundary diffusion type RE-Fe-B rare earth magnet and preparation method thereof | |
| CN112758950A (en) | Boron alkene nanosheet and preparation method thereof | |
| CN110670107A (en) | Titanium carbide nanosheet/carbon nanotube electromagnetic shielding film and preparation method thereof | |
| KR20130022358A (en) | Carbon material coated with metal or metal oxide and a manufacturing method thereof | |
| CN116397228A (en) | Method for preparing alloy/tantalum carbide composite coating on graphite surface | |
| CN111822308B (en) | CeO (CeO)2Modified nano Ag whisker doped graphene film and preparation method thereof | |
| CN1807233A (en) | Chemical shearing method for preparing high dispersion short carbon nanometer tube | |
| CN112809458B (en) | Silicon carbide wafer and method for processing same | |
| CN110204214A (en) | A kind of preparation method of graphene-based film | |
| CN110540190A (en) | high-heat-conduction heat-dissipation composite film and preparation method thereof | |
| CN114715884B (en) | Construction method of Z-axis heat conduction enhanced graphene heat conduction film, graphene heat conduction film and application of graphene heat conduction film | |
| CN114934387B (en) | High-heat-conductivity carbon fiber and continuous preparation method | |
| CN111484017A (en) | Method for preparing SiC nanoparticles based on silica microspheres @ C | |
| CN114835163B (en) | Novel tungsten sulfide photo-thermal material for water purification and preparation and application thereof | |
| KR20040053240A (en) | Hydrophilic Treatment of a carbon Fiber Construction | |
| EP4148165B1 (en) | Method for preparing heat dissipation component with high flexibility made of graphite or graphene material | |
| CN107313102B (en) | A kind of preparation method of aluminium base graphene, carbon nanotube composite heat dissipation material | |
| CN113652626B (en) | Method for realizing low-temperature nitriding of steel parts with complex shapes | |
| CN114101675A (en) | High-entropy alloy-based self-lubricating composite material and preparation method thereof | |
| KR102651157B1 (en) | Method for Preparing Metal-Carbon Laminate Having High Thermal Conductivity Using Hydrophilic Polymer, Laminate Prepared Thereby and Heat Dissipation Material Comprising Same | |
| CN115282989B (en) | Preparation method of ultrasonic-microwave water environment reconstruction iodine-doped carbon nanotube and iodine-doped carbon nanotube | |
| CN116606144B (en) | Method for preparing graphene heat-conducting thick film through chemical pre-reduction | |
| CN114197014B (en) | Method for realizing surface nanocrystallization of pure titanium part with complex shape | |
| CN111940721B (en) | Method for loading nano metal oxide or nano metal material on porous carbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |