CN115287491B - AlN and Al2O3 hybrid reinforced copper-based composite material and preparation method thereof - Google Patents

AlN and Al2O3 hybrid reinforced copper-based composite material and preparation method thereof Download PDF

Info

Publication number
CN115287491B
CN115287491B CN202210962844.9A CN202210962844A CN115287491B CN 115287491 B CN115287491 B CN 115287491B CN 202210962844 A CN202210962844 A CN 202210962844A CN 115287491 B CN115287491 B CN 115287491B
Authority
CN
China
Prior art keywords
aln
powder
copper
temperature
preparation
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
Application number
CN202210962844.9A
Other languages
Chinese (zh)
Other versions
CN115287491A (en
Inventor
安占涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangxi Boqin Nanomaterials Co ltd
Original Assignee
Jiangxi Boqin Nanomaterials Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jiangxi Boqin Nanomaterials Co ltd filed Critical Jiangxi Boqin Nanomaterials Co ltd
Priority to CN202210962844.9A priority Critical patent/CN115287491B/en
Publication of CN115287491A publication Critical patent/CN115287491A/en
Application granted granted Critical
Publication of CN115287491B publication Critical patent/CN115287491B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B22F1/12—Metallic powder containing non-metallic particles
    • 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
    • B22F1/142—Thermal or thermo-mechanical treatment
    • 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
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • 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
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/16—Both compacting and sintering in successive or repeated steps
    • 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
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0005—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with at least one oxide and at least one of carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • 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
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • 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
    • Y02P10/25—Process efficiency

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Ceramic Products (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Abstract

The invention belongs to the technical field of metal matrix composite materials, and in particular relates to AlN and Al 2 O 3 A hybrid reinforced copper-based composite material and a preparation method thereof. The invention provides AlN and Al 2 O 3 The preparation method of the hybrid reinforced copper-based composite material comprises the following steps of plating copper-plated AlN particles and nanoscale Cu 2 Ball milling and mixing O particles, and mixing with Cu-Al alloy powder and micron-sized Cu 2 Mixing O powder, compacting, presintering, re-compacting and re-sintering to obtain AlN and Al 2 O 3 Hybrid reinforced copper-based composite materials. The density of the composite material prepared by the invention can reach more than 98 percent; wherein nano-sized, dispersed Al is coherent with the matrix 2 O 3 The particles provide high softening temperature resistance for the material, and AlN with high micron size, high volume fraction and good combination with a matrix interface provides good wear resistance, thermal expansion coefficient and heat conduction performance for the material.

Description

AlN and Al2O3 hybrid reinforced copper-based composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of metal matrix composite materials, and in particular relates to AlN and Al 2 O 3 A hybrid reinforced copper-based composite material and a preparation method thereof.
Background
The electronic industry rapidly develops, and electronic components must have higher integration level, faster running speed and larger capacity, and more heat needs to be dissipated, so that higher requirements are put forward on the electronic packaging material, and the electronic packaging material has good mechanical properties, corrosion resistance, electrical insulation performance, thermal cycling dimensional stability, high thermal conductivity, low thermal expansion coefficient and the like. Copper and copper alloy have good heat and electrical conductivity, corrosion resistance, welding, easy forming and moderate price, and are one of the basic materials in the field of electronic packaging.
Aluminum nitride has high thermal conductivity (320W/mK), low linear expansion coefficient (4.84X10 -6 K) and very small densities (3.26 g/cm 3 ) Thus, alN particles are certainly an ideal reinforcement for copper and its alloys, and can well compensate for the performance defects of the matrix. However, the wettability between AlN and copper is poor, high density is difficult to obtain by adopting a material prepared by a conventional powder metallurgy mode, the existence of a large number of pores leads to lower heat conduction performance of the AlN/Cu-based composite material which is actually prepared, and the mechanical strength of the composite material is limited to be improved.
Copper-based composite materials often adopt copper or copper alloy powder as raw materials, and finally the prepared material consists of hard particles and a copper/copper alloy matrix, wherein the copper/copper alloy matrix is easy to soften under high temperature conditions, and particularly under high temperature and high load conditions, the bearing capacity is obviously reduced, the strength and the heat resistance are insufficient, and the copper/copper alloy matrix is easy to soften and deform under high temperature.
Disclosure of Invention
Therefore, the invention aims to solve the technical problems that the copper/copper alloy matrix in the prior art is easy to soften under the high temperature condition, particularly under the high temperature and high load condition, the bearing capacity is obviously reduced, the strength and the heat resistance are insufficient, and the deformation defect is easy to soften under the high temperature, thereby providing the AlN and the Al 2 O 3 A hybrid reinforced copper-based composite material and a preparation method thereof.
Therefore, the invention provides the following technical proposal,
the invention provides AlN and Al 2 O 3 The preparation method of the hybrid reinforced copper-based composite material comprises the following steps,
copper-plated AlN particles and nanoscale Cu 2 Ball milling and mixing O particles, and mixing with Cu-Al alloy powder and micron-sized Cu 2 Mixing O powder to obtain mixed powder, then compacting, presintering, re-compacting and re-sintering to obtain AlN and Al 2 O 3 Hybrid reinforced copper-based composite materials.
Optionally, at least one of the following (1) - (8) is satisfied:
(1) The pressure of the pressed compact is 350-600MPa;
(2) The time of the pressed compact is 30-60s;
(3) The presintering temperature is 868-872 ℃;
(4) The presintering time is 240-540min;
(5) The pressure of the re-pressing is 450-700MPa;
(6) The time of the re-pressing is 30-60s;
(7) The temperature of the re-firing is 1021-1025 ℃;
(8) The re-firing time is 180-480min.
Optionally, during presintering, arranging mutually communicated hollow high-chemical-stability pipelines in a furnace chamber of the sintering furnace, and filling Ni-P alloy in the middle, wherein the eutectic temperature of the Ni-P alloy is consistent with the presintering temperature;
and/or arranging mutually communicated hollow pipelines with high chemical stability in the furnace chamber of the sintering furnace during re-sintering, and filling Co-P alloy in the middle, wherein the eutectic temperature of the Co-P alloy is consistent with the re-sintering temperature.
The Ni content in the Ni-P alloy is 81a.t%, and the P content is 19a.t%;
and/or the Co content in the Co-P alloy is 80.1a.t.% and the P content is 19.9a.t.%.
Optionally, the copper-plated AlN particles and nano Cu 2 O particles, cu-Al alloy powder and micron-sized Cu 2 The mass ratio of the O powder is (0.93-5.85): (0.11-0.7): (931. -98.9): (0.07-0.36).
Optionally, the ball milling time is 24-36h.
Optionally, annealing the powder prior to said compacting;
the temperature of the annealing treatment is 300-400 ℃;
the heat preservation time of the annealing treatment is 120-240min.
Optionally, during ball milling, a control agent is also added;
the control agent is stearic acid;
or, the control agent is stearic acid and polypropylene;
or, the control agent is stearic acid and paraffin;
the mass ratio of the mixed powder to the control agent is (99-96): (1-4).
The mass ratio of the stearic acid to the polypropylene is (80-90): (20-10);
the mass ratio of the stearic acid to the paraffin is (80-90): (20-10);
optionally, the preparation method is performed under an atmosphere of protective gas;
the protective gas includes, but is not limited to, argon.
Optionally, the AlN particles are subjected to cleaning, sensitization and activation treatment before copper plating.
The invention also provides AlN and Al prepared by the preparation method 2 O 3 Hybrid reinforced copper-based composite materials.
The technical scheme of the present invention will be specifically described below,
(1) AlN particle copper plating
Firstly, preparing a plating solution. The raw materials and the proportion are as follows: copper sulfate pentahydrate (24 g/L), sodium potassium tartrate (30 g/L), disodium ethylenediamine tetraacetate (20 g/L), and formaldehyde (15 mol/L), sodium hydroxide (12 g/L).
Then, pretreatment is performed. The AlN ceramic particles are subjected to cleaning, sensitization, activation and the like. Cleaning: the AlN powder was washed with an acetone solution for 15 minutes, and 10g/L NaCO was used 3 、10g/L NaPO 3 2g/L NaOH (2 mol/L) solution of OP emulsifier is washed for 5min at 55 ℃, and then is washed by distilled water; sensitization: placing the cleaned AlN powder into a solution containing 5g/L SnCl 2 ·2H 2 In a sensitization solution prepared by O and 5mL/L HCl (the ratio of the powder to the sensitization solution is 1kg of powder to 2L of sensitization solution), stirring for 20min at room temperature, filtering out, and washing with distilled water; activating: placing the powder into an activating solution (the activating solution comprises 2g/L AgNO) 3 And 25% ammonia water, wherein the ratio of the activating solution to the powder is as follows: 1kg of powder was mixed with 2.5L of an activating solution) and stirred for 10min, filtered off and washed with distilled water.
And finally, carrying out electroless copper plating on the AlN ceramic particles. Putting AlN particles into a plating solution, controlling the temperature to be 45+/-2 ℃, stirring while plating copper, monitoring the pH change of the plating solution in real time, and keeping the pH value of the plating solution between 12.5 and 12.7 by supplementing NaOH solution, wherein the plating time is 1.5h; and (3) within 10min after electroless copper plating is finished, putting the copper-plated powder into 3g/L benzotriazole passivation solution, stirring for 25min, washing with distilled water, and dehydrating with alcohol to obtain copper-plated AlN particles.
(2) Mixing and compacting
Ball milling and mixing: copper-plated AlN particles and nano Cu are firstly plated 2 O particles are subjected to high-energy ball milling mixing, and Cu is promoted 2 The O particles are inlaid in the copper coating on the surfaces of the AlN particles, so that preparation is made for sintering the composite material. The hard alloy ball milling tank is adopted, the grinding balls are matched by adopting big and small balls, and the quantity ratio of the grinding balls with different diameters is phi 8mm: phi 6mm: Φ4mm=1: 3:4, adding a control agent into the ball-milling tank, vacuumizing the ball-milling tank before ball milling, filling high-purity argon as protective gas, repeating the steps for 3 times, sealing, and performing ball milling at the speed of 450r/min, reversing once for two hours, wherein the total time is 20h, and stopping for 30min every 2h to reduce the temperature of the ball-milling tank in order to prevent the temperature of the ball-milling tank from rising too high in the mechanical alloying process. Then ball-milling the powder, cu-Al alloy powder and micron Cu by adopting a V-shaped mixing mode 2 The O powder is thoroughly mixed and ready for powder compaction.
Compacting: the powder is annealed to eliminate work hardening of the powder, the annealing temperature is 350 ℃, high-purity argon is used for protection, the temperature is kept for 2 hours, and a low-boiling point process control agent (stearic acid) is volatilized to avoid adverse effect on the material performance. And compacting the powder under the conditions of 600MPa and 60s of dwell time to obtain a green body.
(3) Sintering:
argon is used for protection, argon is introduced for 10min before heating, then heating is carried out, the heating rate is controlled to be about 10 ℃/min, and then the blank is sintered under the high temperature condition to prepare AlN+Al 2 O 3 Hybrid reinforced Cu-based composites. Presintering at 870 deg.C for 5 hr to promote part of Cu 2 O reacts with Cu-Al alloy to generate nano-grade Al 2 O 3 In the furnace chamberThe middle is provided with mutually communicated hollow high-chemical-stability pipelines, and the middle is filled with Ni-19at.% P alloy fragments, wherein the eutectic temperature of the fragments is 870 ℃ and is consistent with the presintering temperature; after the sample is cooled along with the furnace, the sample is re-pressed under 700MPa, then re-burned, the re-burned temperature is 1023 ℃, the re-burned time is 4 hours, mutually communicated and hollow pipelines with high chemical stability are arranged in the furnace chamber, co-19.9at.% P alloy is filled in the middle, and the eutectic temperature is 1023 ℃ and is consistent with the re-burned temperature.
The technical proposal provided by the invention has the following advantages,
1. the invention provides AlN and Al 2 O 3 The preparation method of the hybrid reinforced copper-based composite material comprises the following steps of plating copper-plated AlN particles and nanoscale Cu 2 Ball milling and mixing O particles, and mixing with Cu-Al alloy powder and micron-sized Cu 2 Mixing O powder, compacting, presintering, re-compacting and re-sintering to obtain AlN and Al 2 O 3 Hybrid reinforced copper-based composite materials.
In the ball milling process of the invention, nano Cu 2 The O particles can be more easily embedded in the copper coating on the AlN surface and are coated by the coating so as to be physically isolated from the Cu-Al alloy powder which is added subsequently. In the presintering process, micron-sized Cu 2 O reacts with Cu (matrix) -Al alloy to generate nano-sized Al in situ inside copper matrix through internal oxidation 2 O 3 Wherein, nano-sized and dispersed Al 2 O 3 The particles are coherent with the matrix copper. Then, in the re-pressing and re-firing process, the nano-scale Cu coated in the copper plating layer 2 Conversion of O particles and copper of copper plating layer to Cu+Cu 2 O eutectic forms an interface structure AlN- (Cu+Cu) 2 O eutectic) -Cu, the eutectic contains Cu which is the same element as the matrix Cu and has good wettability, and the eutectic contains Cu 2 O and AlN have good wettability, interface combination between AlN and copper is obviously improved, and the density of the composite material can reach more than 98%; in situ generation of nano-sized Al inside copper matrix 2 O 3 The particle and micron AlN hybrid reinforced copper-based composite material provides high softening temperature resistance, micron size, high volume fraction andthe AlN with good combination of the matrix interface provides good wear resistance, thermal expansion coefficient and heat conduction performance for the material.
2. AlN and Al provided by the invention 2 O 3 The preparation method of the hybrid reinforced copper-based composite material adopts a twice sintering method when sintering, the presintering temperature is 868-872 ℃, the mutually communicated hollow pipelines are arranged in the furnace chamber of the sintering furnace, the Ni-P alloy is filled in the middle, the presintering temperature is 1021-1025 ℃, the mutually communicated hollow pipelines are arranged in the furnace chamber of the sintering furnace, and the Co-P alloy is filled in the middle. The temperature of the alloy with the eutectic composition can not be increased until the solid phase in the eutectic is completely converted into the liquid phase, and correspondingly, the temperature of the alloy with the eutectic composition can not be reduced until the liquid phase in the eutectic is completely converted into the solid phase, so that the problem of nonuniform temperature in a furnace chamber during sintering can be solved, and the composite material with stable quality can be prepared in batches.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The present embodiment provides an AlN and Al 2 O 3 The preparation method of the hybrid reinforced copper-based composite material comprises the following steps,
(1) AlN particle copper plating
Firstly, preparing a plating solution. The raw materials and the proportion are as follows: copper sulfate pentahydrate (24 g/L), sodium potassium tartrate (30 g/L), disodium ethylenediamine tetraacetate (20 g/L), and formaldehyde (15 mol/L), sodium hydroxide (12 g/L).
Then, pretreatment is performed. The AlN ceramic particles are subjected to cleaning, sensitization, activation and the like. Cleaning: the AlN powder was washed with an acetone solution for 15 minutes, and 10g/L NaCO was used 3 、10g/L NaPO 3 2g/L NaOH (2 mol/L) solution of OP emulsifier is washed for 5min at 55 ℃, and then is washed by distilled water; sensitization: placing the cleaned AlN powder into a solution containing 5g/L SnCl 2 ·2H 2 In a sensitization solution prepared by O and 5mL/L HCl (the ratio of the powder to the sensitization solution is 1kg of powder to 2L of sensitization solution), stirring for 20min at room temperature, filtering out, and washing with distilled water; activating: placing the powder into an activating solution (the activating solution comprises 2g/L AgNO) 3 And 25% ammonia water, wherein the ratio of the activating solution to the powder is as follows: 1kg of powder was mixed with 2.5L of an activating solution) and stirred for 10min, filtered off and washed with distilled water.
And finally, carrying out electroless copper plating on the AlN ceramic particles. Putting AlN particles into a plating solution, controlling the temperature to be 45+/-2 ℃, stirring while plating copper, monitoring the pH change of the plating solution in real time, and keeping the pH value of the plating solution between 12.5 and 12.7 by supplementing NaOH solution, wherein the plating time is 1.5h; and (3) within 10min after electroless copper plating is finished, putting the copper-plated powder into 3g/L benzotriazole passivation solution, stirring for 25min, washing with distilled water, and dehydrating with alcohol to obtain copper-plated AlN particles.
(2) Mixing and compacting
Ball milling and mixing: firstly, 0.093kg of copper-plated AlN particles and 0.011kg of nano Cu are mixed 2 O particles are subjected to high-energy ball milling and mixing, then a hard alloy ball milling tank is adopted, grinding balls are matched by adopting large and small balls, and the number ratio of the grinding balls with different diameters is phi 8mm: phi 6mm: Φ4mm=1: 3:4, ball-material ratio is 10:1, 0.150kg of stearic acid is added as a control agent, the ball-milling tank is vacuumized before ball milling, high-purity argon is filled as protective gas, the ball-milling is repeated for 3 times, sealing is carried out, ball-milling rotating speed is 450r/min, reverse rotation is carried out for two hours, total time is 20 hours, and shutdown is carried out for 30 minutes every 2 hours. Then ball-milling the powder and 9.890kg of Cu-Al alloy powder and 0.007kg of micron Cu by adopting a V-shaped mixing mode 2 The O powder is thoroughly mixed and ready for powder compaction.
Compacting: and (3) carrying out annealing treatment on the powder, wherein the annealing temperature is 300 ℃, the high-purity argon is used for protecting, and the temperature is kept for 120min. Compacting the powder under the conditions of 350MPa and 30s of dwell time to obtain a green body.
(3) Sintering:
argon is used for protection, argon is introduced for 10min before heating, then heating is carried out, the heating rate is controlled to be about 10 ℃/min, and then the blank is sintered under the high temperature condition to prepare AlN+Al 2 O 3 Hybrid reinforced Cu-based composites. Presintering at 870 deg.C for 240min to promote part of Cu 2 O reacts with Cu-Al alloy to generate nano-grade Al 2 O 3 Arranging mutually communicated hollow high-chemical-stability pipelines in a furnace chamber, and filling Ni-19at.% P alloy fragments in the middle, wherein the eutectic temperature is 870 ℃ and is consistent with the presintering temperature; after the sample is cooled along with the furnace, the sample is re-pressed for 30s under 450MPa, then re-firing is carried out, the re-firing temperature is 1023 ℃, the re-firing time is 180min, mutually communicated and hollow pipelines with high chemical stability are arranged in the furnace chamber, co-19.9at.% P alloy is filled in the middle, and the eutectic temperature is 1023 ℃ and is consistent with the re-firing temperature.
Example 2
The present embodiment provides an AlN and Al 2 O 3 The preparation method of the hybrid reinforced copper-based composite material comprises the following steps,
(1) AlN particle copper plating
Firstly, preparing a plating solution. The raw materials and the proportion are as follows: copper sulfate pentahydrate (24 g/L), sodium potassium tartrate (30 g/L), disodium ethylenediamine tetraacetate (20 g/L), and formaldehyde (15 mol/L), sodium hydroxide (12 g/L).
Then, pretreatment is performed. The AlN ceramic particles are subjected to cleaning, sensitization, activation and the like. Cleaning: the AlN powder was washed with an acetone solution for 15 minutes, and 10g/L NaCO was used 3 、10g/L NaPO 3 2g/L NaOH (2 mol/L) solution of OP emulsifier is washed for 5min at 55 ℃, and then is washed by distilled water; sensitization: placing the cleaned AlN powder into a solution containing 5g/L SnCl 2 ·2H 2 In a sensitization solution prepared by O and 5mL/L HCl (the ratio of the powder to the sensitization solution is 1kg of powder to 2L of sensitization solution), stirring for 20min at room temperature, filtering out, and washing with distilled water; activating: placing the powderInto an activating solution (the activating solution comprises 2g/L AgNO) 3 And 25% ammonia water, wherein the ratio of the activating solution to the powder is as follows: 1kg of powder was mixed with 2.5L of an activating solution) and stirred for 10min, filtered off and washed with distilled water.
And finally, carrying out electroless copper plating on the AlN ceramic particles. Putting AlN particles into a plating solution, controlling the temperature to be 45+/-2 ℃, stirring while plating copper, monitoring the pH change of the plating solution in real time, and keeping the pH value of the plating solution between 12.5 and 12.7 by supplementing NaOH solution, wherein the plating time is 1.5h; and (3) within 10min after electroless copper plating is finished, putting the copper-plated powder into 3g/L benzotriazole passivation solution, stirring for 25min, washing with distilled water, and dehydrating with alcohol to obtain copper-plated AlN particles.
(2) Mixing and compacting
Ball milling and mixing: firstly, 0.190kg of copper-plated AlN particles and 0.023kg of nano Cu are mixed 2 O particles are subjected to high-energy ball milling and mixing, then a hard alloy ball milling tank is adopted, grinding balls are matched by adopting large and small balls, and the number ratio of the grinding balls with different diameters is phi 8mm: phi 6mm: Φ4mm=1: 3:4, ball-material ratio is 10:1, 0.204kg of stearic acid is added as a control agent, the ball-milling tank is vacuumized before ball milling, high-purity argon is filled as protective gas, the ball-milling is repeated for 3 times, sealing is carried out, ball-milling rotating speed is 450r/min, reverse rotation is carried out for two hours, total time is 20 hours, and shutdown is carried out for 30 minutes every 2 hours. Then ball-milling the powder, 9.770kg of Cu-Al alloy powder and 0.013kg of micron Cu by adopting a V-shaped mixing mode 2 The O powder is thoroughly mixed and ready for powder compaction.
Compacting: and (3) carrying out annealing treatment on the powder, wherein the annealing temperature is 320 ℃, the high-purity argon is used for protecting, and the temperature is kept for 145min. And compacting the powder under the conditions of 400MPa of pressure and 30s of dwell time to obtain a green body.
(3) Sintering:
argon is used for protection, argon is introduced for 10min before heating, then heating is carried out, the heating rate is controlled to be about 10 ℃/min, and then the blank is sintered under the high temperature condition to prepare AlN+Al 2 O 3 Hybrid reinforced Cu-based composites. Presintering at 870 deg.C for 300min to promote part of Cu 2 O reacts with Cu-Al alloy to generate nano-grade Al 2 O 3 Arranging mutually communicated hollow high-chemical-stability pipelines in a furnace chamber, and filling Ni-19at.% P alloy fragments in the middle, wherein the eutectic temperature is 870 ℃ and is consistent with the presintering temperature; after the sample is cooled along with the furnace, the sample is re-pressed for 40s under the pressure of 500MPa, then re-firing is carried out, the re-firing temperature is 1023 ℃, the re-firing time is 240min, mutually communicated and hollow pipelines with high chemical stability are arranged in the furnace chamber, co-19.9at.% P alloy is filled in the middle, and the eutectic temperature is 1023 ℃ and is consistent with the re-firing temperature.
Example 3
The present embodiment provides an AlN and Al 2 O 3 The preparation method of the hybrid reinforced copper-based composite material comprises the following steps,
(1) AlN particle copper plating
Firstly, preparing a plating solution. The raw materials and the proportion are as follows: copper sulfate pentahydrate (24 g/L), sodium potassium tartrate (30 g/L), disodium ethylenediamine tetraacetate (20 g/L), and formaldehyde (15 mol/L), sodium hydroxide (12 g/L).
Then, pretreatment is performed. The AlN ceramic particles are subjected to cleaning, sensitization, activation and the like. Cleaning: the AlN powder was washed with an acetone solution for 15 minutes, and 10g/L NaCO was used 3 、10g/L NaPO 3 2g/L NaOH (2 mol/L) solution of OP emulsifier is washed for 5min at 55 ℃, and then is washed by distilled water; sensitization: placing the cleaned AlN powder into a solution containing 5g/L SnCl 2 ·2H 2 In a sensitization solution prepared by O and 5mL/L HCl (the ratio of the powder to the sensitization solution is 1kg of powder to 2L of sensitization solution), stirring for 20min at room temperature, filtering out, and washing with distilled water; activating: placing the powder into an activating solution (the activating solution comprises 2g/L AgNO) 3 And 25% ammonia water, wherein the ratio of the activating solution to the powder is as follows: 1kg of powder was mixed with 2.5L of an activating solution) and stirred for 10min, filtered off and washed with distilled water.
And finally, carrying out electroless copper plating on the AlN ceramic particles. Putting AlN particles into a plating solution, controlling the temperature to be 45+/-2 ℃, stirring while plating copper, monitoring the pH change of the plating solution in real time, and keeping the pH value of the plating solution between 12.5 and 12.7 by supplementing NaOH solution, wherein the plating time is 1.5h; and (3) within 10min after electroless copper plating is finished, putting the copper-plated powder into 3g/L benzotriazole passivation solution, stirring for 25min, washing with distilled water, and dehydrating with alcohol to obtain copper-plated AlN particles.
(2) Mixing and compacting
Ball milling and mixing: firstly, 0.310kg of copper-plated AlN particles and 0.037kg of nano Cu are mixed 2 O particles are subjected to high-energy ball milling and mixing, then a hard alloy ball milling tank is adopted, grinding balls are matched by adopting large and small balls, and the number ratio of the grinding balls with different diameters is phi 8mm: phi 6mm: Φ4mm=1: 3:4, ball-material ratio is 10:1, 0.309kg of stearic acid is added as a control agent, the ball-milling tank is vacuumized before ball milling, high-purity argon is filled as protective gas, the ball-milling is repeated for 3 times, sealing is carried out, ball-milling rotating speed is 450r/min, reverse rotation is carried out for two hours, total time is 20 hours, and shutdown is carried out for 30 minutes every 2 hours. Then ball-milling the powder, 9.630kg of Cu-Al alloy powder and 0.020kg of micron Cu by adopting a V-shaped mixing mode 2 The O powder is thoroughly mixed and ready for powder compaction.
Compacting: the powder is annealed at 340 ℃ under the protection of high-purity argon and kept for 165 min. Compacting the powder under the conditions of 450MPa and 40s of dwell time to obtain a green body.
(3) Sintering:
argon is used for protection, argon is introduced for 10min before heating, then heating is carried out, the heating rate is controlled to be about 10 ℃/min, and then the blank is sintered under the high temperature condition to prepare AlN+Al 2 O 3 Hybrid reinforced Cu-based composites. Presintering at 870 deg.C for 360min to promote part of Cu 2 O reacts with Cu-Al alloy to generate nano-grade Al 2 O 3 Arranging mutually communicated hollow high-chemical-stability pipelines in a furnace chamber, and filling Ni-19at.% P alloy fragments in the middle, wherein the eutectic temperature is 870 ℃ and is consistent with the presintering temperature; after the sample is cooled along with the furnace, the sample is re-pressed for 40s under 550MPa, then re-firing is carried out, the re-firing temperature is 1023 ℃, the re-firing time is 300min, mutually communicated and hollow pipelines with high chemical stability are arranged in the furnace chamber, co-19.9at.% P alloy is filled in the middle, and the eutectic temperature is 1023 ℃ and is consistent with the re-firing temperature.
Example 4
The embodiment provides alN and Al 2 O 3 The preparation method of the hybrid reinforced copper-based composite material comprises the following steps,
(1) AlN particle copper plating
Firstly, preparing a plating solution. The raw materials and the proportion are as follows: copper sulfate pentahydrate (24 g/L), sodium potassium tartrate (30 g/L), disodium ethylenediamine tetraacetate (20 g/L), and formaldehyde (15 mol/L), sodium hydroxide (12 g/L).
Then, pretreatment is performed. The AlN ceramic particles are subjected to cleaning, sensitization, activation and the like. Cleaning: the AlN powder was washed with an acetone solution for 15 minutes, and 10g/L NaCO was used 3 、10g/L NaPO 3 2g/L NaOH (2 mol/L) solution of OP emulsifier is washed for 5min at 55 ℃, and then is washed by distilled water; sensitization: placing the cleaned AlN powder into a solution containing 5g/L SnCl 2 ·2H 2 In a sensitization solution prepared by O and 5mL/L HCl (the ratio of the powder to the sensitization solution is 1kg of powder to 2L of sensitization solution), stirring for 20min at room temperature, filtering out, and washing with distilled water; activating: placing the powder into an activating solution (the activating solution comprises 2g/L AgNO) 3 And 25% ammonia water, wherein the ratio of the activating solution to the powder is as follows: 1kg of powder was mixed with 2.5L of an activating solution) and stirred for 10min, filtered off and washed with distilled water.
And finally, carrying out electroless copper plating on the AlN ceramic particles. Putting AlN particles into a plating solution, controlling the temperature to be 45+/-2 ℃, stirring while plating copper, monitoring the pH change of the plating solution in real time, and keeping the pH value of the plating solution between 12.5 and 12.7 by supplementing NaOH solution, wherein the plating time is 1.5h; and (3) within 10min after electroless copper plating is finished, putting the copper-plated powder into 3g/L benzotriazole passivation solution, stirring for 25min, washing with distilled water, and dehydrating with alcohol to obtain copper-plated AlN particles.
(2) Mixing and compacting
Ball milling and mixing: 0.390kg of copper-plated AlN particles and 0.047kg of nano Cu are firstly mixed 2 O particles are subjected to high-energy ball milling and mixing, then a hard alloy ball milling tank is adopted, grinding balls are matched by adopting large and small balls, and the number ratio of the grinding balls with different diameters is phi 8mm: phi 6mm: Φ4mm=1: 3:4, ball material ratio is 10:1, 0.410kg of stearic acid is added as a control agent, the ball milling tank is vacuumized before ball milling, then high-purity argon is filled as protective gas, the sealing is carried out after repeating for 3 times, and the ball milling rotating speed is set450r/min, reversing for one time every two hours, and stopping for 30min every 2 hours for 20 hours. Then ball-milling the powder and 9.540kg of Cu-Al alloy powder and 0.026kg of micron Cu by adopting a V-shaped mixing mode 2 The O powder is thoroughly mixed and ready for powder compaction.
Compacting: the powder is annealed at 360 ℃ under the protection of high-purity argon, and the temperature is kept for 190 min. And compacting the powder under the conditions of 500MPa and 40s of dwell time to obtain a green body.
(3) Sintering:
argon is used for protection, argon is introduced for 10min before heating, then heating is carried out, the heating rate is controlled to be about 10 ℃/min, and then the blank is sintered under the high temperature condition to prepare AlN+Al 2 O 3 Hybrid reinforced Cu-based composites. Presintering at 870 deg.C for 420min to promote part of Cu 2 O reacts with Cu-Al alloy to generate nano-grade Al 2 O 3 Arranging mutually communicated hollow high-chemical-stability pipelines in a furnace chamber, and filling Ni-19at.% P alloy fragments in the middle, wherein the eutectic temperature is 870 ℃ and is consistent with the presintering temperature; after the sample is cooled along with the furnace, the sample is re-pressed for 60 seconds under the pressure of 600MPa, then re-firing is carried out, the re-firing temperature is 1023 ℃, the sintering time is 360 minutes, mutually communicated and hollow pipelines with high chemical stability are arranged in the furnace chamber, co-19.9at.% P alloy is filled in the middle, and the eutectic temperature is 1023 ℃ and is consistent with the re-firing temperature.
Example 5
The present embodiment provides an AlN and Al 2 O 3 The preparation method of the hybrid reinforced copper-based composite material comprises the following steps,
(1) AlN particle copper plating
Firstly, preparing a plating solution. The raw materials and the proportion are as follows: copper sulfate pentahydrate (24 g/L), sodium potassium tartrate (30 g/L), disodium ethylenediamine tetraacetate (20 g/L), and formaldehyde (15 mol/L), sodium hydroxide (12 g/L).
Then, pretreatment is performed. The AlN ceramic particles are subjected to cleaning, sensitization, activation and the like. Cleaning: the AlN powder was washed with an acetone solution for 15 minutes, and 10g/L NaCO was used 3 、10g/L NaPO 3 2g/L NaOH (2 mol/L) solution of OP emulsifier is washed for 5min at 55 ℃, and then is washed by distilled water; sensitization: placing the cleaned AlN powder into a solution containing 5g/L SnCl 2 ·2H 2 In a sensitization solution prepared by O and 5mL/L HCl (the ratio of the powder to the sensitization solution is 1kg of powder to 2L of sensitization solution), stirring for 20min at room temperature, filtering out, and washing with distilled water; activating: placing the powder into an activating solution (the activating solution comprises 2g/L AgNO) 3 And 25% ammonia water, wherein the ratio of the activating solution to the powder is as follows: 1kg of powder was mixed with 2.5L of an activating solution) and stirred for 10min, filtered off and washed with distilled water.
And finally, carrying out electroless copper plating on the AlN ceramic particles. Putting AlN particles into a plating solution, controlling the temperature to be 45+/-2 ℃, stirring while plating copper, monitoring the pH change of the plating solution in real time, and keeping the pH value of the plating solution between 12.5 and 12.7 by supplementing NaOH solution, wherein the plating time is 1.5h; and (3) within 10min after electroless copper plating is finished, putting the copper-plated powder into 3g/L benzotriazole passivation solution, stirring for 25min, washing with distilled water, and dehydrating with alcohol to obtain copper-plated AlN particles.
(2) Mixing and compacting
Ball milling and mixing: first, 0.475kg of copper-plated AlN particles and 0.057kg of nano Cu are mixed 2 O particles are subjected to high-energy ball milling and mixing, then a hard alloy ball milling tank is adopted, grinding balls are matched by adopting large and small balls, and the number ratio of the grinding balls with different diameters is phi 8mm: phi 6mm: Φ4mm=1: 3:4, ball-material ratio is 10:1, 0.150kg of stearic acid is added as a control agent, the ball-milling tank is vacuumized before ball milling, high-purity argon is filled as protective gas, the ball-milling is repeated for 3 times, sealing is carried out, ball-milling rotating speed is 450r/min, reverse rotation is carried out for two hours, total time is 20 hours, and shutdown is carried out for 30 minutes every 2 hours. Then ball-milling the powder, 9.440kg of Cu-Al alloy powder and 0.030kg of micron Cu by adopting a V-shaped mixing mode 2 The O powder is thoroughly mixed and ready for powder compaction.
Compacting: and (3) carrying out annealing treatment on the powder, wherein the annealing temperature is 380 ℃, the high-purity argon is used for protecting, and the temperature is kept for 210min. And compacting the powder under the conditions of 550MPa and 60s of dwell time to obtain a green body.
(3) Sintering:
by argon atmosphereProtecting, introducing argon for 10min before heating, controlling the heating rate to be about 10 ℃/min, and sintering the blank at high temperature to prepare AlN+Al 2 O 3 Hybrid reinforced Cu-based composites. Presintering at 870 deg.C for 480min to promote part of Cu 2 O reacts with Cu-Al alloy to generate nano-grade Al 2 O 3 Arranging mutually communicated hollow high-chemical-stability pipelines in a furnace chamber, and filling Ni-19at.% P alloy fragments in the middle, wherein the eutectic temperature is 870 ℃ and is consistent with the presintering temperature; after the sample is cooled along with the furnace, the sample is re-pressed for 60s under 650MPa, then re-firing is carried out, the re-firing temperature is 1023 ℃, the re-firing time is 420min, mutually communicated and hollow pipelines with high chemical stability are arranged in the furnace chamber, co-19.9at.% P alloy is filled in the middle, and the eutectic temperature is 1023 ℃ and is consistent with the re-firing temperature.
Example 6
The present embodiment provides an AlN and Al 2 O 3 The preparation method of the hybrid reinforced copper-based composite material comprises the following steps,
(1) AlN particle copper plating
Firstly, preparing a plating solution. The raw materials and the proportion are as follows: copper sulfate pentahydrate (24 g/L), sodium potassium tartrate (30 g/L), disodium ethylenediamine tetraacetate (20 g/L), and formaldehyde (15 mol/L), sodium hydroxide (12 g/L).
Then, pretreatment is performed. The AlN ceramic particles are subjected to cleaning, sensitization, activation and the like. Cleaning: the AlN powder was washed with 10g/LNaCO in an acetone solution for 15min 3 、10g/L NaPO 3 2g/L NaOH (2 mol/L) solution of OP emulsifier is washed for 5min at 55 ℃, and then is washed by distilled water; sensitization: placing the cleaned AlN powder into a solution containing 5g/L SnCl 2 ·2H 2 In a sensitization solution prepared by O and 5mL/L HCl (the ratio of the powder to the sensitization solution is 1kg of powder to 2L of sensitization solution), stirring for 20min at room temperature, filtering out, and washing with distilled water; activating: placing the powder into an activating solution (the activating solution comprises 2g/L AgNO) 3 And 25% ammonia water, wherein the ratio of the activating solution to the powder is as follows: 1kg of powder was mixed with 2.5L of an activating solution) and stirred for 10min, filtered off and washed with distilled water.
And finally, carrying out electroless copper plating on the AlN ceramic particles. Putting AlN particles into a plating solution, controlling the temperature to be 45+/-2 ℃, stirring while plating copper, monitoring the pH change of the plating solution in real time, and keeping the pH value of the plating solution between 12.5 and 12.7 by supplementing NaOH solution, wherein the plating time is 1.5h; and (3) within 10min after electroless copper plating is finished, putting the copper-plated powder into 3g/L benzotriazole passivation solution, stirring for 25min, washing with distilled water, and dehydrating with alcohol to obtain copper-plated AlN particles.
(2) Mixing and compacting
Ball milling and mixing: firstly, copper-plated AlN particles of 0.585kg and nano Cu of 0.070kg are mixed 2 O particles are subjected to high-energy ball milling and mixing, then a hard alloy ball milling tank is adopted, grinding balls are matched by adopting large and small balls, and the number ratio of the grinding balls with different diameters is phi 8mm: phi 6mm: Φ4mm=1: 3:4, ball-material ratio is 10:1, 0.150kg of stearic acid is added as a control agent, the ball-milling tank is vacuumized before ball milling, high-purity argon is filled as protective gas, the ball-milling is repeated for 3 times, sealing is carried out, ball-milling rotating speed is 450r/min, reverse rotation is carried out for two hours, total time is 20 hours, and shutdown is carried out for 30 minutes every 2 hours. Then ball-milling the powder and 9.310kg of Cu-Al alloy powder and 0.036kg of micron Cu by adopting a V-shaped mixing mode 2 The O powder is thoroughly mixed and ready for powder compaction.
Compacting: and (3) carrying out annealing treatment on the powder, wherein the annealing temperature is 400 ℃, the high-purity argon is used for protecting, and the temperature is kept for 240min. And compacting the powder under the conditions of 600MPa and 60s of dwell time to obtain a green body.
(3) Sintering:
argon is used for protection, argon is introduced for 10min before heating, then heating is carried out, the heating rate is controlled to be about 10 ℃/min, and then the blank is sintered under the high temperature condition to prepare AlN+Al 2 O 3 Hybrid reinforced Cu-based composites. Presintering at 870 deg.C for 540min to promote part of Cu 2 O reacts with Cu-Al alloy to generate nano-grade Al 2 O 3 Arranging mutually communicated hollow high-chemical-stability pipelines in a furnace chamber, and filling Ni-19at.% P alloy fragments in the middle, wherein the eutectic temperature is 870 ℃ and is consistent with the presintering temperature; after the sample is cooled along with the furnace, the sample is re-pressed under the pressure of 700MPa for 6 timesAnd (3) 0s, then, re-sintering, wherein the re-pressing temperature is 1023 ℃, the re-pressing time is 480min, mutually communicated hollow pipelines with high chemical stability are arranged in the furnace chamber, and Co-19.9at.% P alloy is filled in the middle, and the eutectic temperature is 1023 ℃ and is consistent with the re-pressing temperature.
Comparative example 1
This comparative example provides an AlN and Al 2 O 3 The preparation method of the hybrid reinforced copper-based composite material comprises the following steps,
(1) AlN particle copper plating
Firstly, preparing a plating solution. The raw materials and the proportion are as follows: copper sulfate pentahydrate (24 g/L), sodium potassium tartrate (30 g/L), disodium ethylenediamine tetraacetate (20 g/L), and formaldehyde (15 mol/L), sodium hydroxide (12 g/L).
Then, pretreatment is performed. The AlN ceramic particles are subjected to cleaning, sensitization, activation and the like. Cleaning: the AlN powder was washed with an acetone solution for 15 minutes, and 10g/L NaCO was used 3 、10g/L NaPO 3 2g/L NaOH (2 mol/L) solution of OP emulsifier is washed for 5min at 55 ℃, and then is washed by distilled water; sensitization: placing the cleaned AlN powder into a solution containing 5g/L SnCl 2 ·2H 2 In a sensitization solution prepared by O and 5mL/L HCl (the ratio of the powder to the sensitization solution is 1kg of powder to 2L of sensitization solution), stirring for 20min at room temperature, filtering out, and washing with distilled water; activating: placing the powder into an activating solution (the activating solution comprises 2g/L AgNO) 3 And 25% ammonia water, wherein the ratio of the activating solution to the powder is as follows: 1kg of powder was mixed with 2.5L of an activating solution) and stirred for 10min, filtered off and washed with distilled water.
And finally, carrying out electroless copper plating on the AlN ceramic particles. Putting AlN particles into a plating solution, controlling the temperature to be 45+/-2 ℃, stirring while plating copper, monitoring the pH change of the plating solution in real time, and keeping the pH value of the plating solution between 12.5 and 12.7 by supplementing NaOH solution, wherein the plating time is 1.5h; and (3) within 10min after electroless copper plating is finished, putting the copper-plated powder into 3g/L benzotriazole passivation solution, stirring for 25min, washing with distilled water, and dehydrating with alcohol to obtain copper-plated AlN particles.
(2) Mixing and compacting
Ball milling and mixing: firstly, 0.093kg of copper-plated AlN particles and 0.011kg of nano Cu are mixed 2 O particles are subjected to high-energy ball milling and mixing, then a hard alloy ball milling tank is adopted, grinding balls are matched by adopting large and small balls, and the number ratio of the grinding balls with different diameters is phi 8mm: phi 6mm: Φ4mm=1: 3:4, ball-material ratio is 10:1, 0.150kg of stearic acid is added as a control agent, the ball-milling tank is vacuumized before ball milling, high-purity argon is filled as protective gas, the ball-milling is repeated for 3 times, sealing is carried out, ball-milling rotating speed is 450r/min, reverse rotation is carried out for two hours, total time is 20 hours, and shutdown is carried out for 30 minutes every 2 hours. Then ball-milling the powder and 9.890kg of Cu-Al alloy powder and 0.007kg of micron Cu by adopting a V-shaped mixing mode 2 The O powder is thoroughly mixed and ready for powder compaction.
Compacting: annealing the powder at 300 deg.c under high purity argon atmosphere for 120 min. Compacting the powder under the conditions of 350MPa and 30s of dwell time to obtain a green body.
Argon is used for protection, argon is introduced for 10min before heating, then heating is carried out, the heating rate is controlled to be about 10 ℃/min, and then the blank is sintered under the high temperature condition to prepare AlN+Al 2 O 3 Hybrid reinforced Cu-based composites. Presintering at 870 deg.C for 540min to promote part of Cu 2 O reacts with Cu-Al alloy to generate nano-grade Al 2 O 3 Arranging mutually communicated hollow high-chemical-stability pipelines in a furnace chamber, and filling Ni-19at.% P alloy fragments in the middle, wherein the eutectic temperature is 870 ℃ and is consistent with the presintering temperature;
comparative example 2
This comparative example provides an AlN and Al 2 O 3 The preparation method of the hybrid reinforced copper-based composite material comprises the following steps,
(1) AlN particle copper plating
Firstly, preparing a plating solution. The raw materials and the proportion are as follows: copper sulfate pentahydrate (24 g/L), sodium potassium tartrate (30 g/L), disodium ethylenediamine tetraacetate (20 g/L), and formaldehyde (15 mol/L), sodium hydroxide (12 g/L).
Then, pretreatment is performed. The AlN ceramic particles are subjected to cleaning, sensitization, activation and the like. Cleaning: the AlN powder was washed with an acetone solution for 15 minutes and 10g/L NaCO 3 、10g/L NaPO 3 2g/L NaOH (2 mol/L) solution of OP emulsifier is washed for 5min at 55 ℃, and then is washed by distilled water; sensitization: placing the cleaned AlN powder into a solution containing 5g/L SnCl 2 ·2H 2 In a sensitization solution prepared by O and 5mL/L HCl (the ratio of the powder to the sensitization solution is 1kg of powder to 2L of sensitization solution), stirring for 20min at room temperature, filtering out, and washing with distilled water; activating: placing the powder into an activating solution (the activating solution comprises 2g/L AgNO) 3 And 25% ammonia water, wherein the ratio of the activating solution to the powder is as follows: 1kg of powder was mixed with 2.5L of an activating solution) and stirred for 10min, filtered off and washed with distilled water.
And finally, carrying out electroless copper plating on the AlN ceramic particles. Putting AlN particles into a plating solution, controlling the temperature to be 45+/-2 ℃, stirring while plating copper, monitoring the pH change of the plating solution in real time, and keeping the pH value of the plating solution between 12.5 and 12.7 by supplementing NaOH solution, wherein the plating time is 1.5h; and (3) within 10min after electroless copper plating is finished, putting the copper-plated powder into 3g/L benzotriazole passivation solution, stirring for 25min, washing with distilled water, and dehydrating with alcohol to obtain copper-plated AlN particles.
(2) Mixing and compacting
Ball milling and mixing: firstly, adopting a hard alloy ball milling tank to carry out copper plating AlN particles of 0.093kg, adopting large and small balls to match grinding balls, wherein the number ratio of the grinding balls with different diameters is phi 8mm: phi 6mm: Φ4mm=1: 3:4, ball-material ratio is 10:1, 0.150kg of stearic acid is added as a control agent, the ball-milling tank is vacuumized before ball milling, high-purity argon is filled as protective gas, the ball-milling is repeated for 3 times, sealing is carried out, ball-milling rotating speed is 450r/min, reverse rotation is carried out for two hours, total time is 20 hours, and shutdown is carried out for 30 minutes every 2 hours. And then fully mixing the ball-milled powder with 9.890kg of Cu-Al alloy powder in a V-shaped mixing mode, so as to prepare a powder compact.
Compacting: annealing the powder at 300 deg.c under high purity argon atmosphere for 120 min. Compacting the powder under the conditions of 350MPa and 30s of dwell time to obtain a green body.
(3) Sintering:
argon is used for protection, argon is introduced for 10min before heating, and then heating is carried out, and the heating rate is controlled at about 10 ℃/minRight, sintering the blank at high temperature to prepare AlN+Al 2 O 3 Hybrid reinforced Cu-based composites. Presintering at 870 deg.C for 240min to promote part of Cu 2 O reacts with Cu-Al alloy to generate nano-grade Al 2 O 3 Arranging mutually communicated hollow high-chemical-stability pipelines in a furnace chamber, and filling Ni-19at.% P alloy fragments in the middle, wherein the eutectic temperature is 870 ℃ and is consistent with the presintering temperature; after the sample is cooled along with the furnace, the sample is re-pressed for 30s under 450MPa, then re-firing is carried out, the re-firing temperature is 1023 ℃, the re-firing time is 180min, mutually communicated and hollow pipelines with high chemical stability are arranged in the furnace chamber, co-19.9at.% P alloy is filled in the middle, and the eutectic temperature is 1023 ℃ and is consistent with the re-firing temperature.
Comparative example 3
This comparative example provides an AlN and Al 2 O 3 The preparation method of the hybrid reinforced copper-based composite material comprises the following steps of providing AlN and Al 2 O 3 The preparation method of the hybrid reinforced copper-based composite material comprises the following steps,
(1) AlN particle copper plating
Firstly, preparing a plating solution. The raw materials and the proportion are as follows: copper sulfate pentahydrate (24 g/L), sodium potassium tartrate (30 g/L), disodium ethylenediamine tetraacetate (20 g/L), and formaldehyde (15 mol/L), sodium hydroxide (12 g/L).
Then, pretreatment is performed. The AlN ceramic particles are subjected to cleaning, sensitization, activation and the like. Cleaning: the AlN powder was washed with an acetone solution for 15 minutes, and 10g/L NaCO was used 3 、10g/L NaPO 3 2g/L NaOH (2 mol/L) solution of OP emulsifier is washed for 5min at 55 ℃, and then is washed by distilled water; sensitization: placing the cleaned AlN powder into a solution containing 5g/L SnCl 2 ·2H 2 In a sensitization solution prepared by O and 5mL/L HCl (the ratio of the powder to the sensitization solution is 1kg of powder to 2L of sensitization solution), stirring for 20min at room temperature, filtering out, and washing with distilled water; activating: placing the powder into an activating solution (the activating solution comprises 2g/L AgNO) 3 And 25% ammonia water, wherein the ratio of the activating solution to the powder is as follows: 1kg of powder and 2.5L of activating solution) are stirred for 10min and filtered off, and distilled water is used for cleaning。
And finally, carrying out electroless copper plating on the AlN ceramic particles. Putting AlN particles into a plating solution, controlling the temperature to be 45+/-2 ℃, stirring while plating copper, monitoring the pH change of the plating solution in real time, and keeping the pH value of the plating solution between 12.5 and 12.7 by supplementing NaOH solution, wherein the plating time is 1.5h; and (3) within 10min after electroless copper plating is finished, putting the copper-plated powder into 3g/L benzotriazole passivation solution, stirring for 25min, washing with distilled water, and dehydrating with alcohol to obtain copper-plated AlN particles.
(2) Mixing and compacting
Ball milling and mixing: firstly, 0.190kg of copper-plated AlN particles and 0.023kg of nano Cu are mixed 2 O particles are subjected to high-energy ball milling and mixing, then a hard alloy ball milling tank is adopted, grinding balls are matched by adopting large and small balls, and the number ratio of the grinding balls with different diameters is phi 8mm: phi 6mm: Φ4mm=1: 3:4, ball-material ratio is 10:1, 0.150kg of stearic acid is added as a control agent, the ball-milling tank is vacuumized before ball milling, high-purity argon is filled as protective gas, the ball-milling is repeated for 3 times, sealing is carried out, ball-milling rotating speed is 450r/min, reverse rotation is carried out for two hours, total time is 20 hours, and shutdown is carried out for 30 minutes every 2 hours. And then fully mixing the ball-milled powder with 9.770kg of pure Cu powder and 20g of micron Al2O3 powder by adopting a V-shaped mixing mode, and preparing a powder compact.
Compacting: the powder is annealed at 320 deg.c under the protection of high purity argon gas for 145 min. And compacting the powder under the conditions of 400MPa of pressure and 30s of dwell time to obtain a green body.
(3) Sintering:
argon is used for protection, argon is introduced for 10min before heating, then heating is carried out, the heating rate is controlled to be about 10 ℃/min, and then the blank is sintered under the high temperature condition to prepare AlN+Al 2 O 3 Hybrid reinforced Cu-based composites. Presintering at 870 deg.C for 300min to promote part of Cu 2 O reacts with Cu-Al alloy to generate nano-grade Al 2 O 3 Arranging mutually communicated hollow high-chemical-stability pipelines in a furnace chamber, and filling Ni-19at.% P alloy fragments in the middle, wherein the eutectic temperature is 870 ℃ and is consistent with the presintering temperature; after the sample is cooled along with the furnace, the sample is cooled inRe-pressing under 500MPa for 40s, and re-sintering at 1023 deg.c for 240min to form hollow high chemical stability pipeline with Co-19.9at.% P alloy filled in the middle and eutectic temperature of 1023 deg.c.
Comparative example 4
This comparative example provides an AlN and Al 2 O 3 The preparation method of the hybrid reinforced copper-based composite material comprises the following steps,
(1) AlN particle copper plating
Firstly, preparing a plating solution. The raw materials and the proportion are as follows: copper sulfate pentahydrate (24 g/L), sodium potassium tartrate (30 g/L), disodium ethylenediamine tetraacetate (20 g/L), and formaldehyde (15 mol/L), sodium hydroxide (12 g/L).
Then, pretreatment is performed. The AlN ceramic particles are subjected to cleaning, sensitization, activation and the like. Cleaning: the AlN powder was washed with an acetone solution for 15 minutes, and 10g/L NaCO was used 3 、10g/L NaPO 3 2g/L NaOH (2 mol/L) solution of OP emulsifier is washed for 5min at 55 ℃, and then is washed by distilled water; sensitization: placing the cleaned AlN powder into a solution containing 5g/L SnCl 2 ·2H 2 In a sensitization solution prepared by O and 5mL/L HCl (the ratio of the powder to the sensitization solution is 1kg of powder to 2L of sensitization solution), stirring for 20min at room temperature, filtering out, and washing with distilled water; activating: placing the powder into an activating solution (the activating solution comprises 2g/L AgNO) 3 And 25% ammonia water, wherein the ratio of the activating solution to the powder is as follows: 1kg of powder was mixed with 2.5L of an activating solution) and stirred for 10min, filtered off and washed with distilled water.
And finally, carrying out electroless copper plating on the AlN ceramic particles. Putting AlN particles into a plating solution, controlling the temperature to be 45+/-2 ℃, stirring while plating copper, monitoring the pH change of the plating solution in real time, and keeping the pH value of the plating solution between 12.5 and 12.7 by supplementing NaOH solution, wherein the plating time is 1.5h; and (3) within 10min after electroless copper plating is finished, putting the copper-plated powder into 3g/L benzotriazole passivation solution, stirring for 25min, washing with distilled water, and dehydrating with alcohol to obtain copper-plated AlN particles.
(2) Mixing and compacting
Ball milling and mixing: first, 0.093kg of copper-plated AlN particles and 0 were mixed.011kg of micron Cu 2 O particles are subjected to high-energy ball milling and mixing, then a hard alloy ball milling tank is adopted, grinding balls are matched by adopting large and small balls, and the number ratio of the grinding balls with different diameters is phi 8mm: phi 6mm: Φ4mm=1: 3:4, ball-material ratio is 10:1, 0.150kg of stearic acid is added as a control agent, the ball-milling tank is vacuumized before ball milling, high-purity argon is filled as protective gas, the ball-milling is repeated for 3 times, sealing is carried out, ball-milling rotating speed is 450r/min, reverse rotation is carried out for two hours, total time is 20 hours, and shutdown is carried out for 30 minutes every 2 hours. Then ball-milling the powder and 9.890kg of Cu-Al alloy powder and 0.007kg of micron Cu by adopting a V-shaped mixing mode 2 The O powder is thoroughly mixed and ready for powder compaction.
Compacting: and (3) carrying out annealing treatment on the powder, wherein the annealing temperature is 300 ℃, the high-purity argon is used for protecting, and the temperature is kept for 120min. Compacting the powder under the conditions of 350MPa and 30s of dwell time to obtain a green body.
(3) Sintering:
argon is used for protection, argon is introduced for 10min before heating, then heating is carried out, the heating rate is controlled to be about 10 ℃/min, and then the blank is sintered under the high temperature condition to prepare AlN+Al 2 O 3 Hybrid reinforced Cu-based composites. Presintering at 870 deg.C for 240min to promote part of Cu 2 O reacts with Cu-Al alloy to generate nano-grade Al 2 O 3 Arranging mutually communicated hollow high-chemical-stability pipelines in a furnace chamber, and filling Ni-19at.% P alloy fragments in the middle, wherein the eutectic temperature is 870 ℃ and is consistent with the presintering temperature; after the sample is cooled along with the furnace, the sample is re-pressed for 30s under 450MPa, then re-firing is carried out, the re-firing temperature is 1023 ℃, the re-firing time is 180min, mutually communicated and hollow pipelines with high chemical stability are arranged in the furnace chamber, co-19.9at.% P alloy is filled in the middle, and the eutectic temperature is 1023 ℃ and is consistent with the re-firing temperature.
Test case
The composites prepared in examples 1-6 and comparative examples 1-5 were tested for the following test items: the composite material has the advantages of electric conductivity, hardness, compactness, softening temperature resistance, heat conductivity and volume abrasion rate.
The method for testing the conductivity of the composite material comprises the following steps: GB/T35392-2017 nondestructive detection conductivity electromagnetic (eddy current) measuring method.
The method for testing the hardness of the composite material comprises the following steps: GB/T4340.1-1999 metal Vickers hardness test.
The method for testing the compactness of the composite material comprises the following steps: actual density measurement method GB/T10421-2002 determination of sintered metal friction material density, density=actual density/theoretical density.
The method for testing the softening temperature resistance of the composite material comprises the following steps: GB/T33370-2016 copper and copper alloy softening temperature measuring method.
The method for testing the thermal conductivity of the composite material comprises the following steps: GBT3651-2008 metal high-temperature heat conductivity coefficient measuring method.
The test method of the thermal expansion coefficient of the composite material comprises the following steps: GB/T4339-1999 determination of the thermal expansion characteristic parameters of metals.
The method for testing the volume abrasion rate of the composite material comprises the following steps: GB-T12444-2006 metal material abrasion test method.
The specific test results are shown in the following table:
as can be seen from the above table, in comparative example 1 and comparative example 1, it is known that the re-firing significantly improves the properties of the material such as density, thermal conductivity, hardness, wear resistance, etc., due to the formation of Cu-Cu between AlN and copper during the re-firing process 2 The O eutectic not only enhances the bonding strength between AlN and copper, but also remarkably improves the wettability. By comparing example 1 with comparative example 2, it can be seen that micron-sized Cu in example 1 2 Addition of O to nano Al 2 O 3 The formation of the material is indispensable, so that the softening temperature resistance of the material is obviously improved, and the performances of the material such as wear resistance, hardness, thermal expansion coefficient and the like are also influenced; on the other hand, nano-scale Cu 2 The addition of O obviously improves the compactness and the heat conductivity of the composite material. By comparing example 2 with comparative example 3, it can be seen that Al 2 O 3 The softening temperature and hardness are obviously reduced by adopting an external particle mode, which is similar to Al 2 O 3 And whether the interface with the matrix is coherent. By comparing example 1 with comparative example 4, it can be seen that all of the micrometer Cu is used 2 O reduces the overall performance of the material, wherein the thermal conductivity and the compactness of the material are mainly affected due to micron-sized Cu 2 O cannot resemble nano-scale Cu 2 O is inlaid in the copper plating layer as well, but mostly participates in Al 2 O 3 Nanoparticle formation, residual Cu 2 O is uniformly distributed in the copper matrix, and Cu-Cu cannot be effectively formed between AlN and copper 2 O eutectic, which fails to improve the problem of poor wettability between AlN and copper, is relatively low in density and thermal conductivity.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims (8)

1. AlN and Al 2 O 3 The preparation method of the hybrid reinforced copper-based composite material is characterized by comprising the following steps of,
copper-plated AlN particles and nanoscale Cu 2 Ball milling and mixing O particles, and mixing with Cu-Al alloy powder and micron-sized Cu 2 Mixing O powder to obtain mixed powder, then compacting, presintering, re-compacting and re-sintering to obtain AlN and Al 2 O 3 A hybrid reinforced copper-based composite, wherein,
the copper-plated AlN particles and nanoscale Cu 2 O particles, cu-Al alloy powder and micron-sized Cu 2 The mass ratio of the O powder is (0.93-5.85): (0.11-0.7): (93.1-98.9): (0.07-0.36);
the pressure of the pressed compact is 350-600MPa;
the time of the pressed compact is 30-60s;
the presintering temperature is 868-872 ℃;
the presintering time is 240-540min;
the pressure of the re-pressing is 450-700MPa;
the time of the re-pressing is 30-60s;
the temperature of the re-firing is 1021-1025 ℃;
the re-firing time is 180-480min.
2. AlN and Al according to claim 1 2 O 3 The preparation method of the hybrid reinforced copper-based composite material is characterized in that,
during presintering, arranging hollow pipelines which are communicated with each other in a furnace chamber of a sintering furnace, and filling Ni-P alloy in the middle, wherein the eutectic temperature of the Ni-P alloy is consistent with the presintering temperature;
and/or arranging hollow pipelines which are communicated with each other in a furnace chamber of the sintering furnace during re-sintering, and filling Co-P alloy in the middle, wherein the eutectic temperature of the Co-P alloy is consistent with the re-sintering temperature.
3. AlN and Al according to claim 1 2 O 3 The preparation method of the hybrid reinforced copper-based composite material is characterized in that the ball milling time is 24-36h.
4. AlN and Al according to claim 1 2 O 3 The preparation method of the hybrid reinforced copper-based composite material is characterized in that the powder is annealed before the compaction;
the temperature of the annealing treatment is 300-400 ℃;
the heat preservation time of the annealing treatment is 2-4h.
5. AlN and Al according to claim 1 or 3 2 O 3 The preparation method of the hybrid reinforced copper-based composite material is characterized in that during ball milling, the preparation method also needs toAdding a control agent;
the control agent is stearic acid;
or, the control agent is stearic acid and polypropylene;
or, the control agent is stearic acid and paraffin;
the mass ratio of the mixed powder to the control agent is (99-96): (1-4).
6. AlN and Al according to claim 1 2 O 3 The preparation method of the hybrid reinforced copper-based composite material is characterized in that the preparation method is carried out in the atmosphere of protective gas;
the protective gas is argon.
7. AlN and Al according to claim 1 2 O 3 The preparation method of the hybrid reinforced copper-based composite material is characterized by further comprising the steps of cleaning, sensitizing and activating AlN particles before copper plating.
8. AlN and Al prepared by the preparation method of any one of claims 1-7 2 O 3 Hybrid reinforced copper-based composite materials.
CN202210962844.9A 2022-08-11 2022-08-11 AlN and Al2O3 hybrid reinforced copper-based composite material and preparation method thereof Active CN115287491B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210962844.9A CN115287491B (en) 2022-08-11 2022-08-11 AlN and Al2O3 hybrid reinforced copper-based composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210962844.9A CN115287491B (en) 2022-08-11 2022-08-11 AlN and Al2O3 hybrid reinforced copper-based composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115287491A CN115287491A (en) 2022-11-04
CN115287491B true CN115287491B (en) 2023-08-18

Family

ID=83828263

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210962844.9A Active CN115287491B (en) 2022-08-11 2022-08-11 AlN and Al2O3 hybrid reinforced copper-based composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115287491B (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004003024A (en) * 2003-05-21 2004-01-08 Hitachi Ltd Composite material, heat slinger for semiconductor device using it, and semiconductor device
US6909185B1 (en) * 1998-12-07 2005-06-21 Hitachi, Ltd. Composite material including copper and cuprous oxide and application thereof
CN102433481A (en) * 2011-12-16 2012-05-02 黑龙江省科学院高技术研究院 AlN-particle-reinforced copper composite heat sink material and preparation method thereof
RU2014100829A (en) * 2014-01-10 2015-07-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Тольяттинский государственный университет" METHOD FOR PRODUCING NANOVISKER STRUCTURES OF COPPER OXIDE
CN109234556A (en) * 2018-09-28 2019-01-18 河南科技大学 A kind of micro-nano multiphase granules enhance the preparation method of Cu-base composites and preparation method thereof, copper alloy raw material powder
CN110343899A (en) * 2019-07-31 2019-10-18 长春工业大学 A kind of Cu-base composites and preparation method thereof of double size hard particles enhancings
CN110983086A (en) * 2019-12-18 2020-04-10 苏州金江铜业有限公司 Internal nitriding preparation method of aluminum nitride dispersion strengthened copper composite material
CN111778421A (en) * 2019-10-28 2020-10-16 河南科技大学 Copper-based composite material and preparation method thereof
CN111876627A (en) * 2020-08-05 2020-11-03 福建臻璟新材料科技有限公司 Composite material containing aluminum nitride powder and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6909185B1 (en) * 1998-12-07 2005-06-21 Hitachi, Ltd. Composite material including copper and cuprous oxide and application thereof
JP2004003024A (en) * 2003-05-21 2004-01-08 Hitachi Ltd Composite material, heat slinger for semiconductor device using it, and semiconductor device
CN102433481A (en) * 2011-12-16 2012-05-02 黑龙江省科学院高技术研究院 AlN-particle-reinforced copper composite heat sink material and preparation method thereof
RU2014100829A (en) * 2014-01-10 2015-07-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Тольяттинский государственный университет" METHOD FOR PRODUCING NANOVISKER STRUCTURES OF COPPER OXIDE
CN109234556A (en) * 2018-09-28 2019-01-18 河南科技大学 A kind of micro-nano multiphase granules enhance the preparation method of Cu-base composites and preparation method thereof, copper alloy raw material powder
CN110343899A (en) * 2019-07-31 2019-10-18 长春工业大学 A kind of Cu-base composites and preparation method thereof of double size hard particles enhancings
CN111778421A (en) * 2019-10-28 2020-10-16 河南科技大学 Copper-based composite material and preparation method thereof
CN110983086A (en) * 2019-12-18 2020-04-10 苏州金江铜业有限公司 Internal nitriding preparation method of aluminum nitride dispersion strengthened copper composite material
CN111876627A (en) * 2020-08-05 2020-11-03 福建臻璟新材料科技有限公司 Composite material containing aluminum nitride powder and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
氮化铝颗粒表面镀铜及其增强铜基复合材料;刘德宝等;《兵器材料科学与工程》;20050331;第28卷(第2期);第8-11页 *

Also Published As

Publication number Publication date
CN115287491A (en) 2022-11-04

Similar Documents

Publication Publication Date Title
Varol et al. The effect of silver coated copper particle content on the properties of novel Cu-Ag alloys prepared by hot pressing method
US5759216A (en) Diamond sintered body having high strength and high wear-resistance and manufacturing method thereof
CN106048275B (en) A kind of preparation method of ceramic phase dispersion strengthening copper alloy
JP2022517021A (en) Method of preparing metal material or metal composite material
CN106904947B (en) Add the self-lubrication ceramic cutter material and preparation method thereof of h-BN@Ni core-shell structure composite granule
CN104630639B (en) A kind of nano silicon nitride yttrium dispersion strengthening iron-base alloy and preparation method
CN105950940B (en) A kind of nickel plating cubic boron nitride material and preparation method thereof
CN110369730B (en) Copper-coated iron powder and preparation method thereof
Pal et al. Investigation of the electroless nickel plated sic particles in sac305 solder matrix
CN105671401A (en) Nanometer tungsten carbide silver contact material and manufacturing method
WO2022011721A1 (en) Powder metallurgy high-speed steel for large-sized complex tool and preparation method therefor
Liu et al. Microstructure and properties of silver-added W-Cu prepared by infiltration sintering
CN110699676A (en) High-strength high-conductivity metal glass composite material and preparation method thereof
CN110229989B (en) Multi-element hard alloy and preparation method thereof
CN109518021B (en) Preparation method of high-strength iron-cobalt-nickel alloy
CN108823444B (en) Short-process preparation method of copper-carbon composite material
CN108517429B (en) Ti2Preparation method of AlC reinforced copper-based composite material
CN115287491B (en) AlN and Al2O3 hybrid reinforced copper-based composite material and preparation method thereof
CN112760539B (en) Modified titanium aluminum carbide composite material, preparation method and application
CN106756906B (en) A kind of preparation method of double coating diamond dusts
CN117721409A (en) Preparation method of high-temperature wear-resistant silicide protection layer on surface of refractory high-entropy alloy
US5455001A (en) Method for manufacturing intermetallic compound
Padmavathi et al. Microwave assisted sintering of Al-Cu-Mg-Si-Sn alloy
CN114182127B (en) High-performance in-situ reinforced titanium-based composite material and preparation process thereof
CN110614381A (en) Preparation method of silver-based graphene electrical contact material and electrical contact material thereof

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