CN114031425A - Metallized ceramic - Google Patents
Metallized ceramic Download PDFInfo
- Publication number
- CN114031425A CN114031425A CN202111546431.4A CN202111546431A CN114031425A CN 114031425 A CN114031425 A CN 114031425A CN 202111546431 A CN202111546431 A CN 202111546431A CN 114031425 A CN114031425 A CN 114031425A
- Authority
- CN
- China
- Prior art keywords
- ceramic
- metal
- silicon nitride
- layer
- nitride ceramic
- 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 79
- 239000002184 metal Substances 0.000 claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 41
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011159 matrix material Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 2
- 238000001465 metallisation Methods 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 2
- 239000011888 foil Substances 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 description 14
- 239000011889 copper foil Substances 0.000 description 7
- 239000013307 optical fiber Substances 0.000 description 5
- 239000012467 final product Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 238000002679 ablation Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- PQJKKINZCUWVKL-UHFFFAOYSA-N [Ni].[Cu].[Ag] Chemical compound [Ni].[Cu].[Ag] PQJKKINZCUWVKL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
Images
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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/88—Metals
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
- C04B41/90—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being a metal
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
- Ceramic Products (AREA)
Abstract
The invention belongs to the technical field of ceramics, and discloses a metallized ceramic. The invention discloses a metallized silicon nitride ceramic structure, which comprises a silicon nitride ceramic matrix and a plurality of metal layers, wherein the matrix is a structure of a body; these metal layers are ablated with a fiber laser to ablate the metal foil onto the substrate. The invention can avoid the cracking and separation of the metallization layer and the ceramic substrate caused by stress, improve the metallization strength and can be widely applied to various metal ceramic sealing.
Description
Technical Field
The invention belongs to the technical field of ceramics, and particularly relates to a metallized ceramic.
Background
The silicon nitride ceramic is an inorganic nonmetal strong covalent bond compound, has the advantages of high specific strength, high specific modulus, high temperature resistance, oxidation resistance, wear resistance, high thermal shock resistance and the like, and has special use value in the working environment with high temperature, high speed and strong corrosive medium. However, due to the disadvantages of large brittleness, low ductility, difficult processing and the like, the application of ceramic materials in engineering is limited to a great extent, parts with large size and complex shape are difficult to manufacture for use, and metal materials have excellent room temperature strength and ductility, and a ceramic-metal composite member is obtained by connecting ceramic and metal, so that the advantages of the ceramic and the metal can be combined, the excellent performance of the ceramic materials can be fully exerted, and the application range of the ceramic is further expanded.
At present, after a finished product is produced, the existing partially metallized silicon nitride ceramic is directly packed into a bundle for transportation, but the ceramic and the metal may be peeled off in the packing process, so that the ceramic may be damaged.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the metallized ceramic with excellent performance to solve the problems, the metallized ceramic structure can be prepared at room temperature, post-treatment is not needed, the cost is low, and the connection strength between the ceramic and the metal material is high.
The above purpose of the invention is realized by the following technical scheme:
a metallized ceramic comprises a ceramic substrate and a metal conducting layer, wherein the ceramic substrate is tightly attached to the metal conducting layer.
Further, the ceramic matrix is a silicon nitride ceramic matrix.
Furthermore, the metal conducting layer is uniform and compact and is well connected with the ceramic matrix.
Further, the metal conductive layer is a single layer or multiple layers.
Further, the metal conductive layer comprises one or a combination of several of copper, silver and nickel.
Furthermore, the metal conducting layer sequentially comprises a metal copper layer, a metal silver layer and a metal nickel layer.
Further, the thickness of each layer of metal of the metal conducting layer is 10-50 μm.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a metallized silicon nitride ceramic structure, which comprises a silicon nitride ceramic matrix and a plurality of metal layers, wherein the matrix is a structure of a body; these metal layers are ablated with a fiber laser to ablate the metal foil onto the substrate.
The invention can avoid the cracking and separation of the metallization layer and the ceramic substrate caused by stress, improve the metallization strength and can be widely applied to various metal ceramic sealing.
The product manufactured by the invention has high connection strength between the ceramic and the metal material, and can adapt to an extremely cold and extremely hot environment.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a schematic structural diagram of an apparatus used in the present invention, wherein parts 1, 2, 3 and 4 are commercially available fiber lasers, part 5 is a workpiece and a target material, and the target material is sputtered onto the workpiece by laser to realize metallization;
FIG. 2 is a schematic structural view of a metallized silicon nitride ceramic prepared according to example 4 of the present invention.
In the figure: 1. the laser processing system comprises a laser control system, 2, a laser parameter regulating system, 3, a focal length, 4, a processing platform, 5, a ceramic substrate, 6, a silicon nitride ceramic substrate, 7, a metal copper layer, 8, a metal silver layer and 9, a metal nickel layer.
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and experimental equipment, materials, reagents and the like used in the experimental method can be obtained from commercial sources.
The optical fiber laser used in the invention is produced by Changchun optical precision machinery and physical research institute of Chinese academy of sciences, New Changchun industry opto-electronic technology Limited company, and has the model number of JK-MAX-50 and the serial number of HPW-YE0560D, and the laser parameter control software is EZCad 2.5.3.
Example 1
The ceramic structure of the present invention is made as follows:
s1, drawing a pattern of a metalized area in EZCad2.5.3 software according to the size of a silicon nitride ceramic matrix 6;
s2, setting a scanning speed of 200mm/s, a scanning interval of 0.02mm and laser power of 800W in software;
s3, placing the silicon nitride ceramic matrix 6 on a processing platform 4, and covering a metal copper foil with the thickness of 10 mu m on the surface of the silicon nitride ceramic matrix to enable the metal copper foil to be tightly attached to the silicon nitride ceramic matrix 6;
and S4, starting a power supply of the optical fiber laser, adjusting the focal length position to perform laser processing until the laser completes one-time scanning according to the path of the pattern of the metalized area, and forming a metal copper layer 7 on the surface of the silicon nitride ceramic substrate 6 to obtain a final product.
After welding at the temperature of 500 ℃ and 300 ℃, the bonding strength is 20 Mpa.
Example 2
The ceramic structure of the present invention is made as follows:
s1, drawing a pattern of a metalized area in EZCad2.5.3 software according to the size of a silicon nitride ceramic matrix 6;
s2, setting a scanning speed of 200mm/s, a scanning interval of 0.02mm and laser power of 800W in software;
s3, placing the silicon nitride ceramic matrix 6 on the processing platform 4, and covering a metal copper foil with the thickness of 10 mu m on the surface of the silicon nitride ceramic matrix to enable the metal copper foil to be tightly attached to the silicon nitride ceramic matrix 6;
s4, starting a power supply of the optical fiber laser, adjusting the focal position to perform laser processing until the laser completes one-time scanning according to the path of the pattern of the metalized area, and forming a metal copper layer 7 on the surface of the silicon nitride ceramic substrate 6;
s5, continuously placing the silicon nitride ceramic on a processing platform 4, and covering a metal silver foil with the thickness of 10 mu m on the surface of the silicon nitride ceramic to enable a metal silver layer 8 to be tightly attached to a metal copper layer 7;
s6, adjusting the focal length position and carrying out laser processing until laser scanning ablation is finished, and forming a copper-silver composite metal layer on the surface of the silicon nitride ceramic substrate 6 to obtain a final product.
After welding at the temperature of 500 ℃ and 300 ℃, the bonding strength is 10 Mpa.
Example 3
The ceramic structure of the present invention is made as follows:
s1, drawing a pattern of a metalized area in EZCad2.5.3 software according to the size of a silicon nitride ceramic matrix 6;
s2, setting a scanning speed of 200mm/s, a scanning interval of 0.02mm and laser power of 800W in software;
s3, placing the silicon nitride ceramic matrix 6 on the processing platform 4, and covering a metal copper foil with the thickness of 10 mu m on the surface of the silicon nitride ceramic matrix to enable the metal copper foil to be tightly attached to the silicon nitride ceramic matrix 6;
s4, starting a power supply of the optical fiber laser, adjusting the focal position to perform laser processing until the laser completes one-time scanning according to the path of the pattern of the metalized area, and forming a metal copper layer 7 on the surface of the silicon nitride ceramic substrate 6;
s5, continuously placing the silicon nitride ceramic on a laser workbench, and covering a metal nickel foil with the thickness of 10 mu m on the surface of the silicon nitride ceramic to enable the metal nickel foil to be tightly attached to the metal copper layer 7;
s6, adjusting the focal length position and carrying out laser processing until laser scanning ablation is finished, and forming a copper-nickel composite metal layer on the surface of the silicon nitride ceramic substrate 6 to obtain a final product.
After welding at the temperature of 500 ℃ and 300 ℃, the bonding strength is 10 Mpa.
The bonding force of examples 1-3 is compared, and the bonding force of the metal copper layer is the best, and the bonding force reaches 20 MPa.
Example 4
The ceramic structure of the present invention is made as follows:
s1, drawing a pattern of a metalized area in EZCad2.5.3 software according to the size of a silicon nitride ceramic matrix 6;
s2, setting a scanning speed of 200mm/s, a scanning interval of 0.02mm and laser power of 800W in software;
s3, placing the silicon nitride ceramic substrate 6 on a working platform, and covering a metal copper foil with the thickness of 10 mu m on the surface of the silicon nitride ceramic substrate to enable the metal copper layer 7 to be tightly attached to the silicon nitride ceramic substrate 6;
s4, starting a power supply of the optical fiber laser, adjusting the focal position to perform laser processing until the laser completes one-time scanning according to the path of the pattern of the metalized area, and forming a metal copper layer 7 on the surface of the silicon nitride ceramic substrate 6;
s5, continuously placing the silicon nitride ceramic on a laser workbench, and covering a metal silver foil with the thickness of 10 mu m on the surface of the silicon nitride ceramic to enable the silver foil to be tightly attached to the metal copper layer 7;
s6, continuously placing the silicon nitride ceramic on a laser workbench, and covering a metal nickel foil with the thickness of 10 mu m on the surface of the silicon nitride ceramic to enable the nickel foil to be tightly attached to the metal silver layer 8;
and S7, adjusting the focal length position and carrying out laser processing until laser scanning ablation is finished, and forming a copper-silver-nickel composite metal layer on the surface of the silicon nitride ceramic to obtain a final product.
After welding at the temperature of 500 ℃ and 300 ℃, the bonding strength is 10 Mpa.
The foregoing examples are provided for illustration and description of the invention only and are not intended to limit the invention to the scope of the described examples. Furthermore, it will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that many variations and modifications may be made in accordance with the teachings of the present invention, which variations and modifications are within the scope of the present invention as claimed.
Claims (6)
1. The metallized ceramic is characterized by comprising a ceramic substrate and a metal conducting layer, wherein the ceramic substrate is tightly attached to the metal conducting layer.
2. The metallized ceramic of claim 1, wherein said ceramic matrix is a silicon nitride ceramic matrix.
3. The metallized ceramic of claim 1, wherein said metallic conductive layer is a single layer or a plurality of layers.
4. The metallized ceramic of claim 1, wherein said conductive metal layer comprises one or a combination of copper, silver and nickel.
5. The metallized ceramic of claim 1, wherein said metallic conductive layer comprises, in order, a metallic copper layer (7), a metallic silver layer (8), and a metallic nickel layer (9).
6. The metallized ceramic of claim 1, wherein each metal thickness of said conductive metal layer is in the range of 10 μm to 50 μm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111546431.4A CN114031425A (en) | 2021-12-16 | 2021-12-16 | Metallized ceramic |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111546431.4A CN114031425A (en) | 2021-12-16 | 2021-12-16 | Metallized ceramic |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114031425A true CN114031425A (en) | 2022-02-11 |
Family
ID=80147016
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111546431.4A Pending CN114031425A (en) | 2021-12-16 | 2021-12-16 | Metallized ceramic |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114031425A (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6437484A (en) * | 1987-08-04 | 1989-02-08 | Nippon Steel Corp | Metallizing of ceramic by active metal |
JPS6437483A (en) * | 1987-08-04 | 1989-02-08 | Nippon Steel Corp | Metallizing of ceramic by alloy comprising noble metal as main component |
CN103880478A (en) * | 2012-12-21 | 2014-06-25 | 比亚迪股份有限公司 | Ceramic surface selective metallization method and ceramic |
CN106413270A (en) * | 2016-11-04 | 2017-02-15 | 大连大学 | Aluminum nitride ceramic circuit board and preparation method thereof |
CN110240494A (en) * | 2019-06-28 | 2019-09-17 | 大连大学 | A kind of fiber reinforcement Cf/SiC composite plate weld connector |
CN111269028A (en) * | 2020-03-05 | 2020-06-12 | 哈尔滨工业大学(威海) | Silicon nitride ceramic surface metallization method |
-
2021
- 2021-12-16 CN CN202111546431.4A patent/CN114031425A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6437484A (en) * | 1987-08-04 | 1989-02-08 | Nippon Steel Corp | Metallizing of ceramic by active metal |
JPS6437483A (en) * | 1987-08-04 | 1989-02-08 | Nippon Steel Corp | Metallizing of ceramic by alloy comprising noble metal as main component |
CN103880478A (en) * | 2012-12-21 | 2014-06-25 | 比亚迪股份有限公司 | Ceramic surface selective metallization method and ceramic |
CN106413270A (en) * | 2016-11-04 | 2017-02-15 | 大连大学 | Aluminum nitride ceramic circuit board and preparation method thereof |
CN110240494A (en) * | 2019-06-28 | 2019-09-17 | 大连大学 | A kind of fiber reinforcement Cf/SiC composite plate weld connector |
CN111269028A (en) * | 2020-03-05 | 2020-06-12 | 哈尔滨工业大学(威海) | Silicon nitride ceramic surface metallization method |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101572586B1 (en) | Layered body and manufacturing method for layered body | |
US10166751B2 (en) | Method for enhanced additive manufacturing | |
US4602731A (en) | Direct liquid phase bonding of ceramics to metals | |
CN101494322B (en) | Tungsten copper connection method | |
CN103469197B (en) | Hard substrate is obtained by laser assisted cold spraying the method for hard particles coating | |
CN102275022B (en) | Connecting method of C/C composite material and copper or copper alloy | |
CN105414762A (en) | Laser connection method based on laser material additive manufacturing technology | |
CN104625629A (en) | Titanium-aluminium alloy blisk and manufacturing method thereof | |
EP0164272A3 (en) | Dual alloy cooled turbine wheel and method for its manufacture | |
CN112775431B (en) | Laser additive manufacturing method of titanium alloy/stainless steel dissimilar metal member | |
JP2013089799A (en) | Manufacturing method of circuit board with heat dissipation fin | |
KR20080038080A (en) | Metal mold for optical device forming and process for producing the same | |
KR20180057662A (en) | LAMINATE AND METHOD FOR MANUFACTURING LAMINATE | |
EP2898980B1 (en) | Method of bonding a metallic component to a non-metallic component using a compliant material | |
CN103612007A (en) | Preparation method of high-temperature alloy three-dimensional lattice sandwich structure | |
CN102732849A (en) | Method for surface modification and high strength connection of magnesium alloy and aluminum alloy | |
CN113523725A (en) | Production method of kovar alloy and oxygen-free copper composite material | |
CN114031425A (en) | Metallized ceramic | |
CN106939378A (en) | The preparation method of non-crystaline amorphous metal/fine copper laminar composite | |
CN107442922A (en) | A kind of method that connecting dissimilar material is spread using amorphous intermediate layer | |
CN113909801A (en) | Preparation method of low-activation steel and tungsten all-solid-solution joint | |
KR910016950A (en) | Manufacturing method of composite material and manufacturing method of hydrothermal material and hydrothermal material | |
US5975410A (en) | Process of bonding a metal brush structure to a planar surface of a metal substrate | |
CN109676234A (en) | A kind of method of nickel base superalloy annular element local diffusion connection Kufil | |
CN103280519B (en) | Minitype thermoelectricity module and manufacture method 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 | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220211 |