CN117263710A - Preparation method of ceramic/metal composite material - Google Patents
Preparation method of ceramic/metal composite material Download PDFInfo
- Publication number
- CN117263710A CN117263710A CN202311298640.0A CN202311298640A CN117263710A CN 117263710 A CN117263710 A CN 117263710A CN 202311298640 A CN202311298640 A CN 202311298640A CN 117263710 A CN117263710 A CN 117263710A
- Authority
- CN
- China
- Prior art keywords
- ceramic
- composite material
- metal composite
- copper
- laser
- 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.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 85
- 239000002905 metal composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000001465 metallisation Methods 0.000 claims abstract description 15
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 14
- 239000011888 foil Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910010293 ceramic material Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000013307 optical fiber Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 4
- 230000007704 transition Effects 0.000 abstract description 4
- 238000003466 welding Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005253 cladding Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
- C04B37/023—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
- C04B2237/12—Metallic interlayers
- C04B2237/123—Metallic interlayers based on iron group metals, e.g. steel
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
- C04B2237/12—Metallic interlayers
- C04B2237/124—Metallic interlayers based on copper
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
The invention belongs to the field of welding, and discloses a preparation method of a ceramic/metal composite material. And (3) rapidly realizing metallization on the surface of the ceramic by laser scanning and marking, and preparing the ceramic/metal composite material by sintering the metallized ceramic and copper through hot isostatic pressing. The method solves the problems that the ceramic and the metal are poor in wettability and are not easy to combine and high in preparation cost, and reduces the cost by carrying out pretreatment on the metal foil on the surface of the ceramic through laser; and the treatment time is short, the process temperature is low, and the operation is safer. In the preferred embodiment of the invention, a transition layer of about 6 mu m exists, the existence of the transition layer can well increase the binding force of the composite material, and the peeling strength can reach 9.94N/mm.
Description
Technical Field
The invention belongs to the field of welding, and relates to a preparation method of a ceramic/metal composite material.
Background
The composite material formed by the ceramic and the copper has excellent mechanical property of the ceramic material and conductivity of the metallic copper, and is widely applied to power devices. However, ceramic materials mainly consist of ionic bonds and covalent bonds, copper consists of metal bonds, and the ceramic and metal copper atomic structures are basically different, so that the ceramic/metal composite material is difficult to prepare due to poor wettability of the ceramic and metal composite material and direct wetting and spreading of copper on the surface of the ceramic material are basically impossible. To address this problem, it is particularly important to combine the ceramic with copper in a suitable manner.
Today, the addition of reactive metal solders or the metallization of ceramic surfaces is two common pretreatment approaches for the preparation of ceramic/metal composites. However, the cost of adding the active metal solder is too high; the method for metallizing the ceramic surface is mainly a physical vapor deposition method, a chemical vapor deposition method, a plasma method and the like, which take a long time and are not suitable for mass industrial production. There is a need for a rapid, efficient, low cost method for preparing ceramic/metal composites.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a ceramic/metal composite material, which aims to solve the problems of poor wettability of ceramic and metal, difficult combination and high preparation cost, and reduces the cost by carrying out pretreatment on a laser metal foil on the surface of the ceramic; and the treatment time is short, the process temperature is low, the operation is safer, and finally, the ceramic/metal composite material with high bonding strength is prepared by hot isostatic pressing sintering.
The above object of the present invention is achieved by the following technical solutions:
a method of preparing a ceramic/metal composite comprising: and (3) rapidly realizing metallization on the surface of the ceramic by laser scanning and marking, and preparing the ceramic/metal composite material by sintering the metallized ceramic and copper through hot isostatic pressing.
Further, the method comprises the following specific steps:
s1, placing the cleaned ceramic substrate on a workbench, covering a layer of metal foil on the surface of the ceramic substrate, drawing a pattern of a corresponding metallization area on laser parameter control software of an optical fiber laser, setting laser parameters, starting marking, and finishing metallization of the ceramic surface after marking is finished.
S2, placing the metallized ceramic and copper into a sheath material for vacuum sheath, placing a sample subjected to vacuum sheath into a hot isostatic pressing sintering furnace for sintering, tightly combining the metallized ceramic and copper, and taking out after sintering, so as to finally prepare the ceramic/metal composite material.
Further, the ceramic in the step S1 may be Si 3 N 4 Any one of AlN or other ceramic materials with the thickness of 0.30-1.00 mm; the metal foil can be copper or nickel, and has a thickness of 0.01-0.03 mm.
Furthermore, the ceramic substrate in the step S1 is respectively put into absolute ethyl alcohol and acetone to be ultrasonically cleaned for 10 minutes, then is washed clean by deionized water, and finally is dried by a blower.
Further, the fiber laser parameter control software of the step S1 is ezcad2.5.3.
Further, the pattern of the metallized area in the step S1 is adjusted and set according to the actual size of the ceramic substrate, and may be set into a circular, rectangular or other pattern; clicking the filling button sets the scan line spacing.
Further, the laser parameters of the step S1 are that the power of the fiber laser is 700-900W, the scanning speed is 50-80 mm/S, and the scanning interval is 0.03-0.05 mm.
Further, the sheathing material in the step S2 can be any one of nickel foil, titanium foil and low Wen Gang, and the thickness is 0.1-0.15 mm; the thickness of copper is 0.1-5.0 mm.
Further, the vacuum packaging in the step S2 is to put the metallized ceramic and copper into packaging materials, and reduce the vacuum degree to 10 by vacuumizing -3 Pa or below.
Further, the step S2 of hot isostatic pressing sintering is to place the sample with the successful sheath into a hot isostatic pressing sintering furnace for sintering, and the sintering process is as follows: (1) raising the temperature from 25 ℃ to 600-700 ℃ at 5-10 ℃/min, raising the pressure to 80-100 MPa, maintaining for 20-30 min, raising the temperature to 750-900 ℃ at 3-5 ℃/min, and raising the pressure to 120-200 MPa; (2) maintaining the temperature and pressure at the highest temperature and pressure for 15-30 min; (3) reducing the temperature to 300-400 ℃ at 5-10 ℃/min; (4) cooling to room temperature along with the furnace.
Further, the furnace cover is opened in the step S2, a sample is taken out, and the jacket is cut off to obtain the ceramic/metal composite material.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the ceramic/metal composite material, a layer of metal foil is covered on the surface of a ceramic substrate, laser scanning etching is carried out, and the metal foil is deposited on the surface of the ceramic to realize ceramic metallization; and (3) carrying out vacuum cladding on the ceramic and copper, and placing a sample subjected to vacuum cladding into a hot isostatic pressing sintering furnace to sinter and metalize the ceramic and copper to be tightly combined to prepare the ceramic/metal composite material. The invention can instantly and rapidly generate a large amount of energy by using laser, the metal foil absorbs the energy, and as the laser beam is deposited on the ceramic surface, the scanning speed is extremely high, the agglomeration time of metal particles is short, so that the bonding phenomenon between particles occurs, and therefore, molten metal is coated on the ceramic surface, and the wetting condition of the ceramic surface is effectively improved. The problem of poor wettability between metal and ceramic is well relieved, and the bonding strength of the ceramic/metal composite material is remarkably improved.
The preparation method provided by the invention can be used for rapidly realizing the metallization of the ceramic surface at normal temperature, improving the surface wettability, reducing the cost, realizing the tight combination of the ceramic and the metallic copper, increasing the wettability of the combination of the ceramic and the copper, and preparing the ceramic/metallic composite material with high bonding strength through hot isostatic pressing sintering. In the preferred embodiment of the invention, a transition layer with the thickness of about 6 mu m exists, the existence of the transition layer can well increase the binding force of the composite material, and the peeling strength can reach 9.94N/mm, which is far higher than that of the prior art. After 50 times of thermal cycles, the combination of the copper layer and the ceramic layer is still very tight, which indicates that the combination of the ceramic with copper after surface metallization can well relieve thermal stress and prolong the service life.
Drawings
The invention is further illustrated by the following figures and examples:
FIG. 1 is an XRD pattern of a ceramic surface according to the invention before and after copper metallization according to example 1.
FIG. 2 is an SEM image of copper metallization of a ceramic surface according to the invention of example 1.
Fig. 3 is an SEM image of the ceramic/metal composite material prepared according to example 1 of the present invention.
FIG. 4 is a line scan spectrum of a ceramic/metal composite material prepared according to example 1 of the present invention; wherein figure (a) is an SEM image, and wherein figure (b) is an energy spectrum of the line passing region of figure (a).
Fig. 5 is an SEM image of the ceramic/metal composite material of comparative example 3 of the present invention.
Detailed Description
The present invention is described in detail below by way of specific examples, but the scope of the present invention is not limited thereto. Unless otherwise specified, the experimental methods used in the present invention are all conventional methods, and all experimental equipment, materials, reagents, etc. used can be obtained from commercial sources.
Example 1
The preparation method of the ceramic/metal composite material comprises the following specific steps:
s1, selecting a size of 10 multiplied by 0.35mm 3 Si of (2) 3 N 4 Ceramic, a layer of 10×10×0.02mm size is placed on the surface 3 Is a copper foil of (2); opening EZCAd2.5.3 software to draw a pattern marked by the needed laser parameters, clicking a filling button, setting the laser parameters, setting the laser power to 900W and scanning the laser at a speedThe degree was 60mm/s and the scanning pitch was 0.03mm.
S2, turning on a power supply of the optical fiber laser, clicking red light to display, placing ceramics and copper foil on a workbench, aligning laser focal distance to a ceramic metallization area, clicking a marking button to start laser processing, and finishing Si after marking 3 N 4 And (5) metallizing the surface of the ceramic.
S3, mixing the metallized ceramic with 10 multiplied by 0.20mm 3 Putting copper into a round titanium foil with a diameter of 125mm and a thickness of 0.10mm for vacuum coating, and reducing the vacuum degree to 10 -3 Pa or below.
S4, placing the sample subjected to vacuum sheathing into a hot isostatic pressing sintering furnace for sintering, wherein the sintering process comprises the following steps: heating from 25 ℃ to 600 ℃ at 10 ℃/min, boosting to 100MPa, maintaining for 20min, heating to 750 ℃ at 5 ℃/min, and boosting to 150MPa; maintaining at the highest temperature and pressure for 30min; reducing the temperature to 300 ℃ at 5 ℃/min; finally, the temperature is reduced to room temperature at 10 ℃/min.
S5, opening a furnace cover, taking out a sample, and cutting off a sheath to obtain the ceramic/metal composite material.
After peel strength testing: the peel strength was 9.94N/mm.
Comparative example 1
Comparative example 1 differs from example 1 in that: the thickness of the copper foil used for surface metallization was 0.001mm, the laser power setting the laser parameters was 600W, the scanning speed was 100mm/s, and the scanning pitch was 0.02mm. The remainder was the same as in example 1.
The method comprises the following steps of: the peel strength was 1.16N/mm.
Comparative example 2
Comparative example 2 is different from example 1 in that: the hot isostatic pressing sintering process comprises the following steps: directly heating to 750 ℃, and boosting to 150MPa; maintaining at the highest temperature and pressure for 30min; reducing the temperature to 300 ℃ at 5 ℃/min; finally, the temperature is reduced to room temperature at 10 ℃/min. The remainder was the same as in example 1.
The method comprises the following steps of: the peel strength was 2.41N/mm.
Comparative example 3
Comparative example 3 is different from example 1 in that:Si 3 N 4 the ceramic surface was not laser metalized. The remainder was the same as in example 1.
Comparison of the comparative examples with the preferred embodiments of the present invention is as follows:
the above-described embodiments are only preferred embodiments of the invention, and not all embodiments of the invention are possible. Any obvious modifications thereof, which would be apparent to those skilled in the art without departing from the principles and spirit of the present invention, should be considered to be included within the scope of the appended claims.
Claims (7)
1. A method for preparing ceramic/metal composite material is characterized in that metallization is rapidly realized on the surface of ceramic by laser scanning and marking, and the ceramic/metal composite material is prepared by sintering metallized ceramic and copper through hot isostatic pressing.
2. The method for preparing the ceramic/metal composite material as claimed in claim 1, wherein the method comprises the following specific steps:
s1, placing the cleaned ceramic substrate on a workbench, covering a layer of metal foil on the surface of the ceramic substrate, drawing a pattern of a corresponding metallization area on laser parameter control software of an optical fiber laser, setting laser parameters, starting marking, and finishing metallization of the ceramic surface after marking is finished;
s2, placing the metallized ceramic and copper into a sheath material for vacuum sheath, placing a sample subjected to vacuum sheath into a hot isostatic pressing sintering furnace for sintering to enable the metallized ceramic and copper to be tightly combined, and taking out after sintering is completed, so that the ceramic/metal composite material is finally prepared.
3. The method for producing a ceramic/metal composite material according to claim 2, wherein the ceramic in the step S1 is Si 3 N 4 Any one of AlN or other ceramic materials with the thickness of 0.30-1.00 mm; the metal foil can be copper or nickel, and has a thickness of 0.01-0.03 mm.
4. The method for preparing a ceramic/metal composite material as claimed in claim 3, wherein the ceramic substrate in the step S1 is respectively put into absolute ethyl alcohol and acetone, respectively, ultrasonically cleaned for 10 minutes, rinsed with deionized water, and finally dried by a blower.
5. The method of claim 4, wherein the laser parameters of step S1, wherein the power of the fiber laser is 700-900W, the scanning speed is 50-80 mm/S, and the scanning interval is 0.03-0.05 mm.
6. The method for preparing a ceramic/metal composite material according to claim 5, wherein the sheathing material in the step S2 is any one of nickel foil, titanium foil and low Wen Gang, and has a thickness of 0.1-0.15 mm; the thickness of copper is 0.1-5.0 mm.
7. The method for preparing a ceramic/metal composite material according to claim 6, wherein the hot isostatic pressing sintering in step S2 is to sinter the sample with a successful sheath in a hot isostatic pressing sintering furnace, and the sintering process is as follows: (1) raising the temperature from 25 ℃ to 600-700 ℃ at 5-10 ℃/min, raising the pressure to 80-100 MPa, maintaining for 20-30 min, raising the temperature to 750-900 ℃ at 3-5 ℃/min, and raising the pressure to 120-200 MPa; (2) maintaining the temperature and pressure at the highest temperature and pressure for 15-30 min; (3) reducing the temperature to 300-400 ℃ at 5-10 ℃/min; (4) cooling to room temperature along with the furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311298640.0A CN117263710A (en) | 2023-10-09 | 2023-10-09 | Preparation method of ceramic/metal composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311298640.0A CN117263710A (en) | 2023-10-09 | 2023-10-09 | Preparation method of ceramic/metal composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117263710A true CN117263710A (en) | 2023-12-22 |
Family
ID=89210232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311298640.0A Pending CN117263710A (en) | 2023-10-09 | 2023-10-09 | Preparation method of ceramic/metal composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117263710A (en) |
-
2023
- 2023-10-09 CN CN202311298640.0A patent/CN117263710A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108520855B (en) | Method for improving reliability of ceramic copper-clad plate by using nano silver paste | |
| CN111454080B (en) | Copper-clad or copper-clad alloy aluminum oxide ceramic substrate and preparation method thereof | |
| CN104105353B (en) | A kind of manufacture method of high-precision ceramic circuit board | |
| CN102248278A (en) | Magnesium alloy and aluminum alloy interlayer diffusion welding method | |
| CN109354512B (en) | Preparation method for chemical copper plating on surface of high-thermal-conductivity silicon nitride ceramic | |
| CN105330340A (en) | Aluminum oxide ceramic metallization method used for brazing | |
| CN102409299B (en) | Preparation method of oxide ceramic sputtering target | |
| CN111889869A (en) | Welding method for high-purity rare earth and alloy target | |
| CN114309596B (en) | Preparation method of high-heat-conductivity surface-metallized diamond/copper composite substrate | |
| CN104588620B (en) | A kind of preparation method of tungsten copper module | |
| CN103011776B (en) | A kind of pottery and preparation method thereof, ceramic composite and preparation method thereof | |
| CN110453214A (en) | A kind of laser cladding method of nickel-base alloy laser cladding powder | |
| CN101862922B (en) | Binary alloy sealing solder wire | |
| CN111269028A (en) | Silicon nitride ceramic surface metallization method | |
| CN112979351A (en) | Multilayer metal film-coated silicon nitride ceramic substrate and preparation method thereof | |
| CN112899607A (en) | Method for coating nickel or nickel alloy on surface of alumina ceramic | |
| CN112830814A (en) | Method for coating copper or copper alloy on surface of aluminum nitride ceramic | |
| CN110335798B (en) | Diamond energy transmission window and preparation method thereof | |
| CN112225567B (en) | Method for preparing molybdenum silicide coating through slurry sintering | |
| CN117263710A (en) | Preparation method of ceramic/metal composite material | |
| CN113939095B (en) | Ceramic copper-clad plate and preparation method thereof | |
| CN105436643A (en) | Direct aluminum or aluminum alloy brazing method for aluminum oxide ceramics | |
| CN104404505B (en) | The spraying preparation method of Cu/Mo/Cu composite sheet | |
| CN114231917B (en) | Preparation method of high-purity rare earth and alloy target material | |
| CN115821211A (en) | Method for preparing diamond/copper composite material at low temperature and high pressure |
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 |