CN116288606B - Tellurium copper composite metal material and processing technology thereof - Google Patents
Tellurium copper composite metal material and processing technology thereof Download PDFInfo
- Publication number
- CN116288606B CN116288606B CN202310328485.6A CN202310328485A CN116288606B CN 116288606 B CN116288606 B CN 116288606B CN 202310328485 A CN202310328485 A CN 202310328485A CN 116288606 B CN116288606 B CN 116288606B
- Authority
- CN
- China
- Prior art keywords
- copper
- tellurium
- nickel
- graphene
- metal material
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/18—Non-metallic particles coated with metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/004—Filling molds with powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1094—Alloys containing non-metals comprising an after-treatment
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The application relates to the technical field of alloy materials, in particular to a tellurium-copper composite metal material and a processing technology thereof. According to the scheme, elements such as tellurium, chromium, lanthanum, yttrium, cerium and the like are introduced into the copper alloy, and the chromium element can be uniformly distributed in a copper matrix in a single-phase form and plays a role in strengthening a second phase to block dislocation movement so as to improve the hardness and tensile strength of the alloy; the rare earth element can be combined with the impurity element to form refractory compound, the alloy melt is purified, and in the copper matrix, the rare earth element mainly exists in a tellurium-rare earth compound state, so that the nucleation of crystal grains is promoted, and the structure is refined; the tellurium copper alloy substrate prepared by the method is suitable in component proportion, and the prepared tellurium copper composite metal material not only has excellent corrosion resistance and wear resistance, but also has excellent high-temperature oxidation resistance, can be plated with silver on the surface of a nickel plating layer in subsequent production, and has higher practicability.
Description
Technical Field
The application relates to the technical field of alloy materials, in particular to a tellurium-copper composite metal material and a processing technology thereof.
Background
With the continuous development of technology, copper alloy has been involved in various fields of aerospace, transportation, power transmission, electronic information and the like. Pure copper has the characteristics of good electric conduction, heat conduction, corrosion resistance and the like, but has the defects that the strength of the pure copper is low, a large amount of engineering material requirements cannot be met, the application range of the pure copper is limited, and therefore, how to improve the comprehensive mechanical properties of the copper alloy is a very important topic for research and development personnel.
Meanwhile, enterprises have certain requirements on the surface corrosion resistance and high-temperature oxidation resistance of copper alloy, but the existing copper metal materials on the market cannot meet the requirements of us, so that based on the situation, the application discloses a tellurium copper composite metal material and a processing technology thereof, and provides a metal material with excellent comprehensive performance.
Disclosure of Invention
The present application is directed to a tellurium-copper composite metal material and a processing technology thereof, so as to solve the problems set forth in the background art.
In order to solve the technical problems, the application provides the following technical scheme:
a tellurium copper composite metal material processing technology comprises the following steps:
(1) Uniformly mixing nickel-plated graphene and tellurium copper powder to form mixed powder;
spreading a layer of tellurium copper powder in a graphite mold, spreading two layers of mixed powder on the surface, horizontally placing for 2-3 min in an externally applied magnetic field environment, and compacting to form a pressed compact;
sintering the pressed compact at 600-610 ℃, crushing after sintering, and sieving to obtain graphene composite powder;
(2) Placing red copper in a smelting furnace, heating to melt under the protection of a covering agent, adding phosphorus copper intermediate alloy, pure tellurium, pure chromium, copper lanthanum intermediate alloy, copper yttrium intermediate alloy and copper cerium intermediate alloy after complete melting, smelting, casting, cold-rolling and forming, and performing heat treatment at 400-500 ℃ for 3-4 hours to obtain a substrate;
(3) And (3) placing the substrate in a plating solution A, and electroplating for 30-40 min at 45-50 ℃ to obtain a finished product.
In the more optimized scheme, in the step (3), the plating solution A comprises the following components: 250-300 g/L of nickel sulfate, 40-45 g/L of nickel chloride, 30-35 g/L of boric acid, 0.1-0.2 g/L of sodium dodecyl sulfate, 4-6 g/L of nickel-plated graphene and 4-6 g/L of graphene composite powder; the pH of the plating solution is 5, and the current density during electroplating is 5A/dm 2 。
In a more optimized scheme, in the step (2), the components of each element of the base material are as follows: tellurium: 0.3 to 0.5 percent of chromium: 0.5 to 0.7 percent of yttrium: 0.2 to 0.3 percent of lanthanum: 0.2 to 0.3 percent of cerium: 0.1 to 0.2 percent of phosphorus: 0.001 to 0.002 percent, and the balance of copper;
the sintering process parameters are as follows: the sintering time is 4-6 min, the sintering pressure is 40-45 MPa, and the heating rate is 45-50 ℃/min.
In the more optimized scheme, in the step (1), the nickel-plated graphene is 0.4-0.6wt% of the mixed powder; the magnetic field intensity of the externally applied magnetic field is 0.2-0.5T, and the radial direction of the graphite mold is consistent with the direction of the externally applied magnetic field; each layer is of the same thickness when tiled.
In the more optimized scheme, in the step (1), the particle size of the graphene composite powder is 60-100 mu m; the tellurium content in the tellurium copper powder is 0.5-0.6wt% and the balance is copper.
In the step (2), the smelting temperature is 1250-1280 ℃ and the casting temperature is 1180-1200 ℃ in a more optimized scheme; flake graphite is used as a covering agent, and magnesium is used as a refining agent.
In the more optimized scheme, in the step (1), the preparation steps of the nickel-plated graphene are as follows:
s1: mixing graphene nano sheets with deionized water, performing ultrasonic dispersion for 20-30 min, filtering, then placing in hydrochloric acid solution of stannous chloride for sensitization, performing ultrasonic dispersion for 20-30 min, filtering, cleaning with deionized water, then transferring into hydrochloric acid solution of palladium chloride for activation, performing ultrasonic dispersion for 20-30 min, cleaning with deionized water after activation, and performing vacuum drying to obtain activated graphene nano sheets;
in the sensitization and activation process, the adding amount of the graphene nano-sheets is 10-15 mg/mL; in hydrochloric acid solution of stannous chloride, the concentration of the stannous chloride is 10g/L, and the concentration of the hydrochloric acid is 40mL/L; in a hydrochloric acid solution of palladium chloride, the concentration of the palladium chloride is 0.5g/L, and the concentration of the hydrochloric acid is 25mL/L;
s2: placing the dried activated graphene nano-sheets into a plating solution B, plating nickel on the surfaces of the activated graphene nano-sheets for 30-40 min at the temperature of 65-70 ℃, carrying out vacuum suction filtration, washing with deionized water, and drying to obtain nickel-plated graphene; when nickel plating is carried out, the addition amount of the activated graphene nano sheet is 5-10 mg/mL.
The more optimized scheme, plating solution B each component quantity is: 25-35 g/L nickel sulfate, 30-40 g/L sodium hypophosphite, 15-20 g/L trisodium citrate, and ammonia water to adjust the pH value to 8.5-9.5.
According to an optimized scheme, the metal material is obtained by processing the tellurium copper composite metal material by the processing technology.
Compared with the prior art, the application has the following beneficial effects:
the application discloses a tellurium copper composite metal material and a processing technology thereof, which are characterized in that elements such as tellurium, chromium, lanthanum, yttrium, cerium and the like are introduced into copper alloy, and are taken as a base material, wherein the chromium element can be uniformly distributed in a copper matrix in a single phase form and plays a role of strengthening a second phase, so that dislocation movement is blocked, and the hardness and the tensile strength of the alloy are improved; the rare earth element can be combined with impurity elements to form refractory compounds, and the alloy melt is purified, wherein in a copper matrix, the rare earth element mainly exists in a tellurium-rare earth compound state to promote crystal grain nucleation and refine a structure, so that based on the above conditions, the application defines that the components of the elements of the substrate are as follows: tellurium: 0.3 to 0.5 percent of chromium: 0.5 to 0.7 percent of yttrium: 0.2 to 0.3 percent of lanthanum: 0.2 to 0.3 percent of cerium: 0.1 to 0.2 percent of phosphorus: 0.001-0.002%, and the balance copper ", the tellurium copper alloy base material prepared under the formula has excellent mechanical property and conductivity, and has higher practical applicability.
Based on the conception, in order to further improve the corrosion resistance and the high-temperature oxidation resistance of the surface of the tellurium copper alloy substrate, nickel is electroplated on the surface of the tellurium copper alloy substrate, and the plating solution adopts 250-300 g/L nickel sulfate, 40-45 g/L nickel chloride, 30-35 g/L boric acid, 0.1-0.2 g/L sodium dodecyl sulfate, 4-6 g/L nickel-plated graphene and 4-6 g/L graphene composite powder; the pH of the plating solution is 5, and the current density during electroplating is 5A/dm < 2 >; in the process, the nickel-plated graphene and graphene composite powder are introduced in the scheme, on one hand, the nickel-plated graphene can be introduced to improve the compactness of a nickel layer, so that the corrosion resistance of the tellurium copper alloy material is improved, the nickel is plated on the surface of the graphene, the nickel-plated graphene is more uniformly dispersed in the nickel-plated layer, the compatibility is more excellent, and the compactness of the nickel layer is higher; on the other hand, the scheme utilizes nickel-plated graphene and graphene composite powder for compounding, the graphene composite powder is prepared by crushing nickel-plated graphene and tellurium copper alloy powder after compounding and compacting, and the nickel-plated graphene and tellurium copper alloy powder are doped into plating solution, so that the combination property of a nickel layer and a base material is excellent, and the corrosion resistance and the high-temperature oxidation resistance of a product are improved.
In the preparation process of the graphene composite powder, nickel-plated graphene is adopted as a component in the scheme, and the reason is that: an external magnetic field is introduced in the compounding process, and the nickel-plated grapheme can be orderly and uniformly arranged under the action of the external magnetic field, so that when in compacting, a scheme comprises firstly paving a layer of tellurium copper powder in a graphite die, then paving two layers of mixed powder on the surface, horizontally placing for 2-3 min under the environment of the external magnetic field, and compacting to form a compacting; the radial direction of the graphite mold is consistent with the direction of the externally applied magnetic field, and under the limitation of the parameters, the graphene composite powder is more uniform in the subsequent crushing process, and the overall corrosion resistance and the surface wear resistance of the product are more excellent.
The application discloses a tellurium copper composite metal material and a processing technology thereof, which are reasonable in technological design and suitable in component proportion of tellurium copper alloy base materials, and the prepared tellurium copper composite metal material not only has excellent corrosion resistance and wear resistance, but also has excellent high-temperature oxidation resistance, can be plated with silver on the surface of a nickel plating layer in subsequent production, and is higher in practicability.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In the embodiment, the diameter of the graphene nano sheet is 1-5 mu m, and the thickness is 5-10 nm; the red copper is T1 red copper, and the purity is more than or equal to 99.5%; the phosphorus-copper intermediate alloy is CuP14; the copper lanthanum intermediate alloy is Cu-20La; the copper yttrium intermediate alloy is Cu-20Y; the copper cerium intermediate alloy is Cu-20Ce.
Example 1: a tellurium copper composite metal material processing technology comprises the following steps:
(1) Mixing graphene nano sheets with deionized water, performing ultrasonic dispersion for 20min, filtering, then placing the mixture in a hydrochloric acid solution of stannous chloride for sensitization, performing ultrasonic dispersion for 20min, performing deionized water cleaning after filtering, then transferring the mixture into a hydrochloric acid solution of palladium chloride for activation, performing ultrasonic dispersion for 20min, performing deionized water cleaning after activation, and performing vacuum drying to obtain activated graphene nano sheets.
In the sensitization and activation process, the adding amount of the graphene nano-sheets is 15mg/mL; in hydrochloric acid solution of stannous chloride, the concentration of the stannous chloride is 10g/L, and the concentration of the hydrochloric acid is 40mL/L; in the hydrochloric acid solution of palladium chloride, the concentration of palladium chloride is 0.5g/L, and the concentration of hydrochloric acid is 25mL/L.
S2: placing the dried activated graphene nano-sheets in a plating solution B, plating nickel on the surfaces of the activated graphene nano-sheets at 65 ℃ for 35min, carrying out vacuum suction filtration, washing with deionized water, and drying to obtain nickel-plated graphene; when nickel plating is carried out, the addition amount of the activated graphene nano sheet is 8mg/mL.
The plating solution B comprises the following components in percentage by weight: 35g/L nickel sulfate, 30g/L sodium hypophosphite, 15g/L trisodium citrate, and ammonia water to adjust the pH to 8.5.
(2) Uniformly mixing nickel-plated graphene and tellurium copper powder to form mixed powder; the nickel-plated graphene is used in an amount of 0.6wt% of the mixed powder. The tellurium content in the tellurium copper powder is 0.5wt%, and the balance is copper.
Spreading a layer of tellurium copper powder in a graphite mold, spreading two layers of mixed powder on the surface, horizontally placing for 2min in an externally applied magnetic field environment, and compacting to form a pressed compact; the magnetic field intensity of the externally-applied magnetic field is 0.5T, and the radial direction of the graphite mold is consistent with the direction of the externally-applied magnetic field; each layer is of the same thickness when tiled.
Sintering the pressed compact at 600 ℃, crushing after sintering, and sieving to obtain graphene composite powder; the sintering process parameters are as follows: the sintering time is 6min, the sintering pressure is 45MPa, and the heating rate is 45 ℃/min. The particle size of the graphene composite powder is 60 mu m.
(2) And (3) placing red copper in a smelting furnace, heating to melt under the protection of a covering agent, adding phosphorus copper intermediate alloy, pure tellurium, pure chromium, copper lanthanum intermediate alloy, copper yttrium intermediate alloy and copper cerium intermediate alloy after complete melting, smelting, casting, cold-rolling and forming, and carrying out heat treatment at 400 ℃ for 4 hours to obtain a base material. Smelting temperature is 1250 ℃, and casting temperature is 1180 ℃; flake graphite is used as a covering agent, and magnesium is used as a refining agent.
The substrate comprises the following element components: tellurium: 0.5%, chromium: 0.6%, yttrium: 0.3%, lanthanum: 0.3%, cerium: 0.2%, phosphorus: 0.002%, the balance being copper.
(3) And (3) placing the substrate in a plating solution A, and electroplating at 45 ℃ for 40min to obtain a finished product.
The plating solution A comprises the following components: 250g/L of nickel sulfate, 45g/L of nickel chloride, 30g/L of boric acid, 0.2g/L of sodium dodecyl sulfate, 4g/L of nickel-plated graphene and 6g/L of graphene composite powder; the pH of the plating solution is 5, and the current density during electroplating is 5A/dm 2 。
Example 2: a tellurium copper composite metal material processing technology comprises the following steps:
(1) Mixing graphene nano sheets with deionized water, performing ultrasonic dispersion for 25min, filtering, then placing the mixture in a hydrochloric acid solution of stannous chloride for sensitization, performing ultrasonic dispersion for 25min, performing deionized water cleaning after filtering, then transferring the mixture into a hydrochloric acid solution of palladium chloride for activation, performing ultrasonic dispersion for 25min, performing deionized water cleaning after activation, and performing vacuum drying to obtain activated graphene nano sheets.
In the sensitization and activation process, the adding amount of the graphene nano-sheets is 15mg/mL; in hydrochloric acid solution of stannous chloride, the concentration of the stannous chloride is 10g/L, and the concentration of the hydrochloric acid is 40mL/L; in the hydrochloric acid solution of palladium chloride, the concentration of palladium chloride is 0.5g/L, and the concentration of hydrochloric acid is 25mL/L.
S2: placing the dried activated graphene nano-sheets in a plating solution B, plating nickel on the surfaces of the activated graphene nano-sheets for 35min at the temperature of 70 ℃, carrying out vacuum suction filtration, washing with deionized water, and drying to obtain nickel-plated graphene; when nickel plating is carried out, the addition amount of the activated graphene nano sheet is 8mg/mL.
The plating solution B comprises the following components in percentage by weight: 35g/L nickel sulfate, 30g/L sodium hypophosphite, 15g/L trisodium citrate, and ammonia water to adjust the pH to 8.5.
(2) Uniformly mixing nickel-plated graphene and tellurium copper powder to form mixed powder; the nickel-plated graphene is used in an amount of 0.6wt% of the mixed powder. The tellurium content in the tellurium copper powder is 0.5wt%, and the balance is copper.
Spreading a layer of tellurium copper powder in a graphite mold, spreading two layers of mixed powder on the surface, horizontally placing for 3min in an externally applied magnetic field environment, and compacting to form a pressed compact; the magnetic field intensity of the externally-applied magnetic field is 0.5T, and the radial direction of the graphite mold is consistent with the direction of the externally-applied magnetic field; each layer is of the same thickness when tiled.
Sintering the pressed compact at 605 ℃, crushing after sintering, and sieving to obtain graphene composite powder; the sintering process parameters are as follows: the sintering time is 5min, the sintering pressure is 45MPa, and the heating rate is 45 ℃/min. The particle size of the graphene composite powder is 60 mu m.
(2) And (3) placing red copper in a smelting furnace, heating to melt under the protection of a covering agent, adding phosphorus copper intermediate alloy, pure tellurium, pure chromium, copper lanthanum intermediate alloy, copper yttrium intermediate alloy and copper cerium intermediate alloy after complete melting, smelting, casting, cold-rolling and forming, and carrying out heat treatment at 400 ℃ for 4 hours to obtain a base material. The smelting temperature is 1260 ℃, and the casting temperature is 1180 ℃; flake graphite is used as a covering agent, and magnesium is used as a refining agent.
The substrate comprises the following element components: tellurium: 0.5%, chromium: 0.6%, yttrium: 0.3%, lanthanum: 0.3%, cerium: 0.2%, phosphorus: 0.002%, the balance being copper.
(3) And (3) placing the substrate in a plating solution A, and electroplating at 50 ℃ for 40min to obtain a finished product.
The plating solution A comprises the following components: 250g/L of nickel sulfate, 45g/L of nickel chloride, 30g/L of boric acid, 0.2g/L of sodium dodecyl sulfate, 4g/L of nickel-plated graphene and 6g/L of graphene composite powder; the pH of the plating solution is 5, and the current density during electroplating is 5A/dm 2 。
Example 3: a tellurium copper composite metal material processing technology comprises the following steps:
(1) Mixing graphene nano sheets with deionized water, performing ultrasonic dispersion for 30min, filtering, then placing the mixture in a hydrochloric acid solution of stannous chloride for sensitization, performing ultrasonic dispersion for 30min, performing deionized water cleaning after filtering, then transferring the mixture into a hydrochloric acid solution of palladium chloride for activation, performing ultrasonic dispersion for 30min, performing deionized water cleaning after activation, and performing vacuum drying to obtain activated graphene nano sheets.
In the sensitization and activation process, the adding amount of the graphene nano-sheets is 15mg/mL; in hydrochloric acid solution of stannous chloride, the concentration of the stannous chloride is 10g/L, and the concentration of the hydrochloric acid is 40mL/L; in the hydrochloric acid solution of palladium chloride, the concentration of palladium chloride is 0.5g/L, and the concentration of hydrochloric acid is 25mL/L.
S2: placing the dried activated graphene nano-sheets in a plating solution B, plating nickel on the surfaces of the activated graphene nano-sheets at 68 ℃ for 35min, carrying out vacuum suction filtration, washing with deionized water, and drying to obtain nickel-plated graphene; when nickel plating is carried out, the addition amount of the activated graphene nano sheet is 8mg/mL.
The plating solution B comprises the following components in percentage by weight: 35g/L nickel sulfate, 30g/L sodium hypophosphite, 15g/L trisodium citrate, and ammonia water to adjust the pH to 8.5.
(2) Uniformly mixing nickel-plated graphene and tellurium copper powder to form mixed powder; the nickel-plated graphene is used in an amount of 0.6wt% of the mixed powder. The tellurium content in the tellurium copper powder is 0.5wt%, and the balance is copper.
Spreading a layer of tellurium copper powder in a graphite mold, spreading two layers of mixed powder on the surface, horizontally placing for 3min in an externally applied magnetic field environment, and compacting to form a pressed compact; the magnetic field intensity of the externally-applied magnetic field is 0.5T, and the radial direction of the graphite mold is consistent with the direction of the externally-applied magnetic field; each layer is of the same thickness when tiled.
Sintering the pressed compact at 610 ℃, crushing after sintering, and sieving to obtain graphene composite powder; the sintering process parameters are as follows: the sintering time is 4min, the sintering pressure is 45MPa, and the heating rate is 45 ℃/min. The particle size of the graphene composite powder is 60 mu m.
(2) And (3) placing red copper in a smelting furnace, heating to melt under the protection of a covering agent, adding phosphorus copper intermediate alloy, pure tellurium, pure chromium, copper lanthanum intermediate alloy, copper yttrium intermediate alloy and copper cerium intermediate alloy after complete melting, smelting, casting, cold-rolling and forming, and carrying out heat treatment at 400 ℃ for 4 hours to obtain a base material. The smelting temperature is 1280 ℃, and the casting temperature is 1180 ℃; flake graphite is used as a covering agent, and magnesium is used as a refining agent.
The substrate comprises the following element components: tellurium: 0.5%, chromium: 0.6%, yttrium: 0.3%, lanthanum: 0.3%, cerium: 0.2%, phosphorus: 0.002%, the balance being copper.
(3) And (3) placing the substrate in a plating solution A, and electroplating at 48 ℃ for 40min to obtain a finished product.
The plating solution A comprises the following components: 250g/L of nickel sulfate, 45g/L of nickel chloride, 30g/L of boric acid, 0.2g/L of sodium dodecyl sulfate, 4g/L of nickel-plated graphene and 6g/L of graphene composite powder; the pH of the plating solution is 5, and the current density during electroplating is 5A/dm 2 。
Comparative example 1: comparative example 1 with example 2 as a control, only nickel plated graphene was introduced into bath a in comparative example 1, with the remaining steps remaining unchanged.
A tellurium copper composite metal material processing technology comprises the following steps:
(1) Mixing graphene nano sheets with deionized water, performing ultrasonic dispersion for 25min, filtering, then placing the mixture in a hydrochloric acid solution of stannous chloride for sensitization, performing ultrasonic dispersion for 25min, performing deionized water cleaning after filtering, then transferring the mixture into a hydrochloric acid solution of palladium chloride for activation, performing ultrasonic dispersion for 25min, performing deionized water cleaning after activation, and performing vacuum drying to obtain activated graphene nano sheets.
In the sensitization and activation process, the adding amount of the graphene nano-sheets is 15mg/mL; in hydrochloric acid solution of stannous chloride, the concentration of the stannous chloride is 10g/L, and the concentration of the hydrochloric acid is 40mL/L; in the hydrochloric acid solution of palladium chloride, the concentration of palladium chloride is 0.5g/L, and the concentration of hydrochloric acid is 25mL/L.
S2: placing the dried activated graphene nano-sheets in a plating solution B, plating nickel on the surfaces of the activated graphene nano-sheets for 35min at the temperature of 70 ℃, carrying out vacuum suction filtration, washing with deionized water, and drying to obtain nickel-plated graphene; when nickel plating is carried out, the addition amount of the activated graphene nano sheet is 8mg/mL.
The plating solution B comprises the following components in percentage by weight: 35g/L nickel sulfate, 30g/L sodium hypophosphite, 15g/L trisodium citrate, and ammonia water to adjust the pH to 8.5.
(2) Uniformly mixing nickel-plated graphene and tellurium copper powder to form mixed powder; the nickel-plated graphene is used in an amount of 0.6wt% of the mixed powder. The tellurium content in the tellurium copper powder is 0.5wt%, and the balance is copper.
Spreading a layer of tellurium copper powder in a graphite mold, spreading two layers of mixed powder on the surface, horizontally placing for 3min in an externally applied magnetic field environment, and compacting to form a pressed compact; the magnetic field intensity of the externally-applied magnetic field is 0.5T, and the radial direction of the graphite mold is consistent with the direction of the externally-applied magnetic field; each layer is of the same thickness when tiled.
Sintering the pressed compact at 605 ℃, crushing after sintering, and sieving to obtain graphene composite powder; the sintering process parameters are as follows: the sintering time is 5min, the sintering pressure is 45MPa, and the heating rate is 45 ℃/min. The particle size of the graphene composite powder is 60 mu m.
(2) And (3) placing red copper in a smelting furnace, heating to melt under the protection of a covering agent, adding phosphorus copper intermediate alloy, pure tellurium, pure chromium, copper lanthanum intermediate alloy, copper yttrium intermediate alloy and copper cerium intermediate alloy after complete melting, smelting, casting, cold-rolling and forming, and carrying out heat treatment at 400 ℃ for 4 hours to obtain a base material. The smelting temperature is 1260 ℃, and the casting temperature is 1180 ℃; flake graphite is used as a covering agent, and magnesium is used as a refining agent.
The substrate comprises the following element components: tellurium: 0.5%, chromium: 0.6%, yttrium: 0.3%, lanthanum: 0.3%, cerium: 0.2%, phosphorus: 0.002%, the balance being copper.
(3) And (3) placing the substrate in a plating solution A, and electroplating at 50 ℃ for 40min to obtain a finished product.
The plating solution A comprises the following components: 250g/L of nickel sulfate, 45g/L of nickel chloride, 30g/L of boric acid, 0.2g/L of sodium dodecyl sulfate and 4g/L of nickel-plated graphene; the pH of the plating solution is 5, and the current density during electroplating is 5A/dm 2 。
Comparative example 2: comparative example 2 in comparative example 2, in which the graphene composite powder was prepared without introducing an external magnetic field, the remaining steps remained unchanged.
A tellurium copper composite metal material processing technology comprises the following steps:
(1) Mixing graphene nano sheets with deionized water, performing ultrasonic dispersion for 25min, filtering, then placing the mixture in a hydrochloric acid solution of stannous chloride for sensitization, performing ultrasonic dispersion for 25min, performing deionized water cleaning after filtering, then transferring the mixture into a hydrochloric acid solution of palladium chloride for activation, performing ultrasonic dispersion for 25min, performing deionized water cleaning after activation, and performing vacuum drying to obtain activated graphene nano sheets.
In the sensitization and activation process, the adding amount of the graphene nano-sheets is 15mg/mL; in hydrochloric acid solution of stannous chloride, the concentration of the stannous chloride is 10g/L, and the concentration of the hydrochloric acid is 40mL/L; in the hydrochloric acid solution of palladium chloride, the concentration of palladium chloride is 0.5g/L, and the concentration of hydrochloric acid is 25mL/L.
S2: placing the dried activated graphene nano-sheets in a plating solution B, plating nickel on the surfaces of the activated graphene nano-sheets for 35min at the temperature of 70 ℃, carrying out vacuum suction filtration, washing with deionized water, and drying to obtain nickel-plated graphene; when nickel plating is carried out, the addition amount of the activated graphene nano sheet is 8mg/mL.
The plating solution B comprises the following components in percentage by weight: 35g/L nickel sulfate, 30g/L sodium hypophosphite, 15g/L trisodium citrate, and ammonia water to adjust the pH to 8.5.
(2) Uniformly mixing nickel-plated graphene and tellurium copper powder to form mixed powder; the nickel-plated graphene is used in an amount of 0.6wt% of the mixed powder. The tellurium content in the tellurium copper powder is 0.5wt%, and the balance is copper.
Spreading a layer of tellurium copper powder in a graphite mold, spreading two layers of mixed powder on the surface, horizontally placing for 3min, and compacting to form a pressed compact; each layer is of the same thickness when tiled.
Sintering the pressed compact at 605 ℃, crushing after sintering, and sieving to obtain graphene composite powder; the sintering process parameters are as follows: the sintering time is 5min, the sintering pressure is 45MPa, and the heating rate is 45 ℃/min. The particle size of the graphene composite powder is 60 mu m.
(2) And (3) placing red copper in a smelting furnace, heating to melt under the protection of a covering agent, adding phosphorus copper intermediate alloy, pure tellurium, pure chromium, copper lanthanum intermediate alloy, copper yttrium intermediate alloy and copper cerium intermediate alloy after complete melting, smelting, casting, cold-rolling and forming, and carrying out heat treatment at 400 ℃ for 4 hours to obtain a base material. The smelting temperature is 1260 ℃, and the casting temperature is 1180 ℃; flake graphite is used as a covering agent, and magnesium is used as a refining agent.
The substrate comprises the following element components: tellurium: 0.5%, chromium: 0.6%, yttrium: 0.3%, lanthanum: 0.3%, cerium: 0.2%, phosphorus: 0.002%, the balance being copper.
(3) And (3) placing the substrate in a plating solution A, and electroplating at 50 ℃ for 40min to obtain a finished product.
The plating solution A comprises the following components: 250g/L of nickel sulfate, 45g/L of nickel chloride, 30g/L of boric acid, 0.2g/L of sodium dodecyl sulfate, 4g/L of nickel-plated graphene and 6g/L of graphene composite powder; the pH of the plating solution is 5, and the current density during electroplating is 5A/dm 2 。
Comparative example 3: comparative example 3 in comparative example 3, in which example 2 was used as a control test, copper powder was used in combination with nickel-plated graphene during the preparation of the graphene composite powder, and the remaining steps were kept unchanged.
The tellurium copper composite metal material processing technology comprises the following specific adjustment steps:
(2) Uniformly mixing nickel-plated graphene and pure copper powder to form mixed powder; the nickel-plated graphene is used in an amount of 0.6wt% of the mixed powder.
Spreading a layer of pure copper powder in a graphite die, spreading two layers of mixed powder on the surface, horizontally placing for 3min in an externally applied magnetic field environment, and compacting to form a pressed compact; the magnetic field intensity of the externally-applied magnetic field is 0.5T, and the radial direction of the graphite mold is consistent with the direction of the externally-applied magnetic field; each layer is of the same thickness when tiled.
Sintering the pressed compact at 605 ℃, crushing after sintering, and sieving to obtain graphene composite powder; the sintering process parameters are as follows: the sintering time is 5min, the sintering pressure is 45MPa, and the heating rate is 45 ℃/min. The particle size of the graphene composite powder is 60 mu m.
Comparative example 4: comparative example 4 in which example 2 was used as a control test, the plating solution a in comparative example 4 was only graphene composite powder, and the remaining steps were kept unchanged.
The tellurium copper composite metal material processing technology comprises the following specific adjustment steps:
(3) And (3) placing the substrate in a plating solution A, and electroplating at 50 ℃ for 40min to obtain a finished product.
The plating solution A comprises the following components: 250g/L of nickel sulfate, 45g/L of nickel chloride, 30g/L of boric acid, 0.2g/L of sodium dodecyl sulfate and 6g/L of graphene composite powder; the pH of the plating solution is 5, and the current density during electroplating is 5A/dm 2 。
Detection experiment:
1. the substrates prepared in examples 1 to 3 were extruded into 16.0mm bars by a TCL400 continuous extrusion machine during processing, drawn to 3.0mm, and heat-treated at 400℃for 4 hours to obtain substrate samples, and the surface resistivity and tensile strength (stretching rate: 2 mm/min) of the substrate samples were measured. As shown in table one.
List one
| Project | Surface resistivity%IACS | Tensile strength MPa |
| Example 1 | 83.16 | 191 |
| Example 2 | 84.72 | 194 |
| Example 3 | 84.37 | 193 |
2. The composite metal materials prepared in examples 1 to 3 and comparative examples 1 to 4 were taken to have a size of 10mm×10mm, and after surface pickling, they were subjected to heat treatment at 600 ℃ for 6 hours, the mass before and after heat treatment was recorded, and the weight gain was calculated.
Taking the composite metal materials prepared in examples 1-3, crisscrossing and drawing 1mm on the nickel layer on the surface of the composite metal material by using stainless steel needles 2 And (3) the large square cells and the small square cells are scratched deep to the tellurium copper alloy substrate, then the tellurium copper alloy substrate is stuck and peeled by using adhesive tape, and whether the surface coating is peeled off or not is observed. (this test is not performed for comparative examples 1-4 and is therefore indicated by "/").
The composite metal materials prepared in examples 1 to 3 and comparative examples 1 to 4 were immersed in a 3.5wt% NaCl solution at 25℃for 7 days, taken out, weighed, and the corrosion rate was calculated from the weight difference before and after corrosion. The specific data are shown in Table two.
Watch II
Conclusion: the application discloses a tellurium copper composite metal material and a processing technology thereof, which are reasonable in technological design and suitable in component proportion of tellurium copper alloy base materials, and the prepared tellurium copper composite metal material not only has excellent corrosion resistance and wear resistance, but also has excellent high-temperature oxidation resistance, can be plated with silver on the surface of a nickel plating layer in subsequent production, and is higher in practicability.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present application, and the present application is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present application has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (7)
1. The processing technology of the tellurium copper composite metal material is characterized by comprising the following steps of: the method comprises the following steps:
(1) Uniformly mixing nickel-plated graphene and tellurium copper powder to form mixed powder; the dosage of the nickel-plated graphene is 0.4-0.6wt% of the mixed powder; the tellurium content in the tellurium copper powder is 0.5-0.6wt% and the balance is copper;
spreading a layer of tellurium copper powder in a graphite mold, spreading two layers of mixed powder on the surface, horizontally placing for 2-3 min in an externally applied magnetic field environment, and compacting to form a pressed compact; the magnetic field strength of the externally applied magnetic field is 0.2-0.5T, and the radial direction of the graphite mold is consistent with the direction of the externally applied magnetic field;
sintering the pressed compact at 600-610 ℃, crushing after sintering, and sieving to obtain graphene composite powder;
(2) Placing red copper in a smelting furnace, heating to melt under the protection of a covering agent, adding phosphorus-copper intermediate alloy, pure tellurium, pure chromium, copper-lanthanum intermediate alloy, copper-yttrium intermediate alloy and copper-cerium intermediate alloy after complete melting, smelting, casting, cold rolling, and heat treating at 400-500 ℃ for 3-4 hours to obtain a substrate;
(3) Placing the substrate in a plating solution A, and electroplating at 45-50 ℃ for 30-40 min to obtain a finished product; the plating solution A comprises the following components: 250-300 g/L of nickel sulfate, 40-45 g/L of nickel chloride, 30-35 g/L of boric acid, 0.1-0.2 g/L of sodium dodecyl sulfate, 4-6 g/L of nickel-plated graphene and 4-6 g/L of graphene composite powder; the pH of the plating solution is 5, and the current density during electroplating is 5A/dm 2 。
2. The process for manufacturing the tellurium copper composite metal material of claim 1, wherein: in the step (2), the components of each element of the base material are as follows: tellurium: 0.3-0.5%, chromium: 0.5-0.7%, yttrium: 0.2-0.3%, lanthanum: 0.2-0.3%, cerium: 0.1-0.2%, phosphorus: 0.001-0.002%, and the balance copper.
3. The process for manufacturing the tellurium copper composite metal material of claim 1, wherein: in the step (1), the particle size of the graphene composite powder is 60-100 mu m; the sintering process parameters are as follows: the sintering time is 4-6 min, the sintering pressure is 40-45 MPa, and the heating rate is 45-50 ℃/min.
4. The process for manufacturing the tellurium copper composite metal material of claim 1, wherein: in the step (2), the smelting temperature is 1250-1280 ℃, and the casting temperature is 1180-1200 ℃.
5. The process for manufacturing the tellurium copper composite metal material of claim 1, wherein: in the step (1), the preparation steps of the nickel-plated graphene are as follows:
s1: sensitization is carried out on the graphene nano-sheets in hydrochloric acid solution of stannous chloride, ultrasonic dispersion is carried out for 20-30 min, deionized water is used for cleaning after filtration, then the graphene nano-sheets are transferred into hydrochloric acid solution of palladium chloride for activation, ultrasonic dispersion is carried out for 20-30 min, deionized water is used for cleaning after activation, and vacuum drying is carried out, so that activated graphene nano-sheets are obtained;
s2: and (3) placing the dried activated graphene nano sheet in a plating solution B, plating nickel on the surface at 65-70 ℃ for 30-40 min, vacuum filtering, washing with deionized water, and drying to obtain the nickel-plated graphene.
6. The process for manufacturing the tellurium copper composite metal material of claim 5, wherein: the plating solution B comprises the following components in percentage by weight: 25-35 g/L nickel sulfate, 30-40 g/L sodium hypophosphite, 15-20 g/L trisodium citrate, and ammonia water to adjust the pH to 8.5-9.5.
7. The metal material obtained by the processing technology of the tellurium copper composite metal material according to any one of claims 1-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310328485.6A CN116288606B (en) | 2023-03-30 | 2023-03-30 | Tellurium copper composite metal material and processing technology thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310328485.6A CN116288606B (en) | 2023-03-30 | 2023-03-30 | Tellurium copper composite metal material and processing technology thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116288606A CN116288606A (en) | 2023-06-23 |
| CN116288606B true CN116288606B (en) | 2023-09-08 |
Family
ID=86801314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310328485.6A Active CN116288606B (en) | 2023-03-30 | 2023-03-30 | Tellurium copper composite metal material and processing technology thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116288606B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106702193A (en) * | 2016-12-02 | 2017-05-24 | 昆明理工大学 | Preparation method of graphene/aluminium composite |
| CN110578065A (en) * | 2019-09-11 | 2019-12-17 | 燕山大学 | Preparation method of graphene reinforced copper-based composite material |
| CN111139461A (en) * | 2020-01-19 | 2020-05-12 | 北京理工大学 | Method for chemically plating nickel on surface of graphene |
| CN113430416A (en) * | 2021-06-21 | 2021-09-24 | 宁波兴敖达金属新材料有限公司 | Lead-free-cutting high-conductivity tellurium-copper alloy material |
| CN115786753A (en) * | 2023-02-02 | 2023-03-14 | 泰州泰锦合金材料有限公司 | Tellurium-copper alloy material containing rare earth metal and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113053606A (en) * | 2021-03-16 | 2021-06-29 | 东莞金坤新材料股份有限公司 | Graphene rare earth permanent magnetic material and preparation method thereof |
-
2023
- 2023-03-30 CN CN202310328485.6A patent/CN116288606B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106702193A (en) * | 2016-12-02 | 2017-05-24 | 昆明理工大学 | Preparation method of graphene/aluminium composite |
| CN110578065A (en) * | 2019-09-11 | 2019-12-17 | 燕山大学 | Preparation method of graphene reinforced copper-based composite material |
| CN111139461A (en) * | 2020-01-19 | 2020-05-12 | 北京理工大学 | Method for chemically plating nickel on surface of graphene |
| CN113430416A (en) * | 2021-06-21 | 2021-09-24 | 宁波兴敖达金属新材料有限公司 | Lead-free-cutting high-conductivity tellurium-copper alloy material |
| CN115786753A (en) * | 2023-02-02 | 2023-03-14 | 泰州泰锦合金材料有限公司 | Tellurium-copper alloy material containing rare earth metal and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "镀镍石墨烯-铝复合材料粉末的分散工艺研究";朱德智 等;《2020年中国铝加工产业年度大会论文集（下册）》;第424-436页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116288606A (en) | 2023-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6490253B2 (en) | Method for preparing graphene / silver composite material | |
| US11834751B2 (en) | Preparation method of copper-based graphene composite with high thermal conductivity | |
| CN104711443A (en) | Graphene/copper composite and preparation method thereof | |
| CN113293424B (en) | Graphene/copper composite powder and preparation method thereof, graphene/copper composite material and preparation method and application thereof | |
| CN111560535A (en) | Preparation method of high-strength graphene/copper composite material | |
| CN113223773B (en) | Second-generation high-temperature superconducting tape and preparation method thereof | |
| CN110684914A (en) | High-strength high-hardness aluminum alloy and preparation method thereof | |
| CN110699676A (en) | High-strength high-conductivity metal glass composite material and preparation method thereof | |
| CN114086013A (en) | High-strength high-conductivity ultrafine-grained tungsten-copper composite material and preparation method thereof | |
| WO2023123859A1 (en) | Graphene/copper composite deformed copper-chromium-zirconium alloy layered strip material, and preparation method therefor | |
| CN116288606B (en) | Tellurium copper composite metal material and processing technology thereof | |
| WO2021027607A1 (en) | Preparation method for highly conductive graphene copper/aluminium composite wire | |
| CN111318689A (en) | Silver-coated copper powder with shell-core structure and preparation method and application thereof | |
| CN112941431A (en) | Powder metallurgy preparation method of fine-particle diamond copper-based composite heat dissipation material | |
| CN115786753B (en) | Tellurium copper alloy material containing rare earth metal and preparation method thereof | |
| CN115652132B (en) | Copper alloy material and application and preparation method thereof | |
| Zuo et al. | Effect of activators on the properties of nickel coated diamond composite powders | |
| CN113199024B (en) | Ternary layered compound, metal-based composite material, and preparation method and raw materials thereof | |
| CN114959814A (en) | Method for quickly electroplating high-conductivity and high-heat-conductivity copper layer | |
| CN111893343A (en) | Modified nano particle dispersion strengthened copper alloy, preparation method and application thereof, electronic component and mechanical component | |
| KR101697941B1 (en) | Manufacturing method of grid for lead-acid battery | |
| CN114409403B (en) | Graphite crucible | |
| CN115044800B (en) | High-strength high-conductivity copper alloy and preparation method thereof | |
| CN113481404B (en) | Surface modified copper bus and preparation method thereof | |
| Osaka et al. | Behavior of the Electroless Composite Films Plated from a Ni‐P Bath with Metallic Dispersion of Zr and Nb Powders |
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 |