CN117466670A - Nickel metal slurry, nickel sintering process and metallized ceramic part - Google Patents
Nickel metal slurry, nickel sintering process and metallized ceramic part Download PDFInfo
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- CN117466670A CN117466670A CN202311249868.0A CN202311249868A CN117466670A CN 117466670 A CN117466670 A CN 117466670A CN 202311249868 A CN202311249868 A CN 202311249868A CN 117466670 A CN117466670 A CN 117466670A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 428
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 183
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 178
- 239000002184 metal Substances 0.000 title claims abstract description 177
- 239000000919 ceramic Substances 0.000 title claims abstract description 113
- 238000005245 sintering Methods 0.000 title claims abstract description 95
- 239000002002 slurry Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000008569 process Effects 0.000 title claims description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 72
- 239000000843 powder Substances 0.000 claims abstract description 52
- 239000002245 particle Substances 0.000 claims abstract description 41
- 238000001465 metallisation Methods 0.000 claims abstract description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000914 Mn alloy Inorganic materials 0.000 claims abstract description 19
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011858 nanopowder Substances 0.000 claims abstract description 16
- PCEXQRKSUSSDFT-UHFFFAOYSA-N [Mn].[Mo] Chemical compound [Mn].[Mo] PCEXQRKSUSSDFT-UHFFFAOYSA-N 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 12
- 230000002209 hydrophobic effect Effects 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 5
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 5
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical group CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 5
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001249 ethyl cellulose Polymers 0.000 claims description 5
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 5
- 229940116411 terpineol Drugs 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000000020 Nitrocellulose Substances 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 229920001220 nitrocellulos Polymers 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000003466 welding Methods 0.000 abstract description 13
- 239000000243 solution Substances 0.000 description 38
- 229910000679 solder Inorganic materials 0.000 description 36
- 238000005219 brazing Methods 0.000 description 26
- 238000000280 densification Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 21
- 238000007789 sealing Methods 0.000 description 18
- 239000002994 raw material Substances 0.000 description 15
- 239000010949 copper Substances 0.000 description 14
- 238000001000 micrograph Methods 0.000 description 14
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 13
- 238000009713 electroplating Methods 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 239000006104 solid solution Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000007480 spreading Effects 0.000 description 5
- 238000003892 spreading Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229910001325 element alloy Inorganic materials 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004630 mental health Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- -1 acrylic acid nitrile Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- UTICYDQJEHVLJZ-UHFFFAOYSA-N copper manganese nickel Chemical compound [Mn].[Ni].[Cu] UTICYDQJEHVLJZ-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 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
- 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
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5144—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the metals of the iron group
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses ceramic metallization slurry, which comprises the following components: nickel powder, sintering aid and binder solution; wherein, the mass ratio of the nickel powder to the binder solution is (1-3): 1, a step of; the mass ratio of the nickel powder to the sintering aid is (80-98): 1, a step of; the sintering aid comprises copper metal powder and manganese metal powder or copper-manganese alloy powder; when the particle diameter d of the nickel powder satisfies the following conditions: when d is more than or equal to 1 mu m and less than or equal to 5 mu m, the sintering aid also comprises nickel nano powder, wherein the particle size of the nickel nano powder is less than 1 mu m, and the mass percentage of each metal element is as follows: mn is less than or equal to 4.5 percent and less than 68 percent; cu is more than or equal to 28.8 and less than 95 percent; ni is more than 0 and less than or equal to 10 percent; when the particle diameter d of the nickel powder is smaller than 1 mu m, the mass percentage of each metal element in the sintering aid is as follows: mn is more than or equal to 5% and less than or equal to 68%; cu is more than or equal to 32% and less than or equal to 95%. The method for sintering nickel on the ceramic surface provided by the invention enhances the compactness of the sintered nickel and improves the welding strength and the airtightness of the metallized ceramic piece.
Description
Technical Field
The invention relates to the technical field of ceramic packaging, in particular to nickel metal slurry, a nickel sintering process and a metallized ceramic piece.
Background
The excellent performance of ceramics and metals can be fully exerted only after the ceramics and the metals are firmly connected, and the success of the connection is based on the reasonable application of the ceramic metallization technology, but the ceramics are often difficult to be directly combined with the metals due to the fact that the atomic structures of the ceramics and the metals are different and the physical and chemical properties are not matched. In the prior art, a molybdenum-manganese metal layer and a nickel metal layer are sequentially coated on the surface of ceramic to metalize the ceramic, and then the ceramic is welded with metal to be welded by using solder. The nickel metal layer has the main functions of enhancing the fluidity of the solder and preventing the solder from diffusing and migrating to the loose porous molybdenum-manganese metal layer during high-temperature brazing, so that the compactness and thickness uniformity of the nickel metal layer directly influence the welding strength, the air tightness and other performances of the ceramic-metal piece to be welded. At present, a nickel metal layer is generally electroplated by a plating method, a thinner and compact nickel metal layer is deposited in molybdenum-manganese metallized ceramic electroplating solution, and then the nickel metal layer is subjected to washing, drying and high-temperature densification treatment. However, the above process inevitably generates waste such as waste liquid and the like to pollute the environment, and corresponding process links and equipment are required to be added for treating three wastes, so that the production cost is increased.
The sintering nickel technology is another nickel coating method, which does not generate electroplating waste liquid, but the nickel metal manufactured by the existing sintering nickel technology is not compact, loose and porous, and directly affects the welding strength and tightness of ceramic-metal pieces to be welded. Therefore, development of a novel ceramic sintering nickel technology which is environment-friendly, low in cost, compact in structure and high in welding reliability is urgently needed.
Disclosure of Invention
The invention provides nickel metal slurry, a nickel sintering process and a metallized ceramic piece, which are used for solving the technical problems that the nickel metal prepared from the existing nickel metal slurry through the nickel sintering process is loose and porous, and the welding strength and the tightness of the metallized ceramic piece are insufficient.
According to one aspect of the present invention, there is provided a ceramic metallizing slurry comprising the following components: nickel powder, sintering aid and binder solution; wherein, the mass ratio of the nickel powder to the binder solution is (1-3): 1, a step of; the mass ratio of the nickel powder to the sintering aid is (80-98): 1, a step of; the sintering aid comprises copper metal powder and manganese metal powder or copper-manganese alloy powder;
when the particle diameter d of the nickel powder satisfies the following conditions: when d is more than or equal to 1 mu m and less than or equal to 5 mu m, the sintering aid also comprises nickel nano powder, wherein the particle size of the nickel nano powder is less than 1 mu m, and the mass percentage of each metal element in the sintering aid is as follows: mn is less than or equal to 4.5 percent and less than 68 percent; cu is more than or equal to 28.8 and less than 95 percent; ni is more than 0 and less than or equal to 10 percent;
when the particle diameter d of the nickel powder is smaller than 1 mu m, the mass percentage of each metal element in the sintering aid is as follows: mn is more than or equal to 5% and less than or equal to 68%; cu is more than or equal to 32% and less than or equal to 95%.
Further, when the sintering aid comprises copper metal powder and manganese metal powder, the particle sizes of the copper metal powder and the manganese metal powder are not more than 10 mu m.
Further, when the sintering aid includes copper-manganese alloy powder, the particle size of the copper-manganese alloy powder is not more than 10 μm.
Further, the binder solution includes an aqueous binder solution or an oily binder solution.
Further, the aqueous binder solution comprises an aqueous binder and water, wherein the binder is a polymer with hydrophilic monomers and hydrophobic monomers, and the mass ratio of the hydrophilic monomers to the hydrophobic monomers is 1: (0.15-18); the mass ratio of the binder to the water is (0.2-1.5): 1.
Further, the oily binder solution comprises an oily binder and an organic solvent, wherein the binder comprises ethyl cellulose or nitrocellulose; the organic solvent is selected from terpineol, diethylene glycol ether acetate, tributyl citrate or tributyl phthalate; the concentration of the oily binder solution is 0.024-0.054 g/mL.
According to another aspect of the present invention, there is also provided a process for sintering nickel, comprising the steps of:
stirring and mixing the nickel powder, the sintering aid and the binder solution at the temperature of 1-90 ℃ to obtain nickel metallization slurry, wherein the viscosity of the nickel metallization slurry is 2500-8000 mPa.s;
and coating the obtained nickel metallization slurry on the surface of the molybdenum-manganese metallized ceramic part, and then drying and sintering to obtain the nickel metal layer.
Further, the drying temperature is 5-80 ℃ and the drying time is 5-120min.
Further, the sintering temperature is 800-1100 ℃; the sintering time is 5-30 min.
In yet another aspect of the present application, a metallized ceramic is provided, comprising a molybdenum manganese metallized ceramic, and a nickel metal layer prepared by the above-described sintered nickel process, wherein the nickel metal layer has a thickness of 0.5-15 μm.
The invention has the following beneficial effects:
when the particle diameter d of the nickel powder satisfies the following conditions: when d is more than or equal to 1 mu m and less than or equal to 5 mu m, copper-manganese alloy (formed by copper and manganese metal powder in a sintering aid or added in the form of copper-manganese alloy powder) is extremely easy to interact with a molybdenum-manganese metal layer with similar structure and composition in the high-temperature sintering process to form a complex multi-element alloy solid solution, and flows and migrates in a molybdenum-manganese metal porous structure to fill holes, so that the compactness of the molybdenum-manganese layer is enhanced. The nickel nano powder in the sintering aid exists in the form of nano nickel powder, and on one hand, the nano nickel powder has a melting point lower than that of the micron nickel powder or nickel components in the alloy are lower than that of the micron nickel powder, so that the contact area between the micron nickel powder particles can be increased, and the transition of the micron nickel powder to a nickel metal layer is promoted. On the other hand, copper metal and manganese metal are easy to interact with nickel metal to form complex alloy solid solution, so that flowing and spreading of the nickel metal on the surface of the molybdenum-manganese metal layer are enhanced, and a nickel metal layer with higher densification degree is formed.
When the grain diameter of the nickel powder is less than 1 mu m, the copper-manganese alloy is extremely easy to interact with a molybdenum-manganese metal layer with similar structure and composition to form a complex multi-element alloy solid solution in the high-temperature sintering process, and flows and migrates in the molybdenum-manganese metal porous structure to fill holes, so that the compactness of the molybdenum-manganese layer is enhanced. The raw material nickel powder is used as nano-scale nickel powder, on one hand, the melting point of the raw material nickel powder is lower than that of micron nickel powder or the nickel component in the alloy is lower than that of micron nickel powder, so that the contact area between nickel powder particles can be increased, the conversion of nickel powder to a nickel metal layer is promoted, on the other hand, copper metal and manganese metal are easy to interact with nickel metal to form a complex alloy solid solution, and the flowing and spreading of nickel metal on the surface of a molybdenum-manganese metal layer are enhanced, so that a nickel metal layer with higher densification degree is formed.
Thus, the sintered nickel process or metallized ceramic provided herein has the following advantages:
(1) The ceramic surface sintering nickel technology provided by the invention is very environment-friendly, and solves the problem of electroplating wastewater pollution existing in the process of electroplating nickel coating.
(2) The method for sintering nickel on the ceramic surface provided by the invention enhances the compactness of the sintered nickel, thereby enhancing the wettability of the solder on the ceramic metal layer and effectively preventing the solder from diffusing and migrating to the loose and porous molybdenum-manganese metal layer during high-temperature brazing.
(3) The densified sintered nickel provided by the invention can effectively reduce the use amount of noble metal solders such as silver, copper and the like, and the cost of raw materials of the solders can be saved by 90% at most.
Taking a ceramic discharge tube product as an example, for a sintered nickel ceramic discharge tube (before densification) without densification and a sintered nickel ceramic discharge tube (after densification) subjected to densification by the technology, the welding strength of the ceramic discharge tube after densification can reach more than 130MPa under the use amount of silver-copper solder with the thickness of 5-10 microns, and the welding strength of the ceramic discharge tube before densification still can only reach about 100MPa under the use amount of silver-copper solder with the thickness of 100 microns.
(4) The slurry preparation process can only use water as a solvent, the water is colorless and odorless, the physical and mental health of production workers cannot be damaged in the drying process, the environment is protected, and the solvent cost is reduced.
(5) The aqueous slurry can be prepared and printed at normal temperature, and the energy consumption cost is reduced.
In addition to the objects, features and advantages described above, the present invention has other objects, features and advantages. The present invention will be described in further detail with reference to the drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a front side electron scanning electron microscope (a low power view, b high power view) of the sintered nickel metal layer in example 1;
FIG. 2 is a cross-sectional electron scanning electron microscope image of the sintered nickel metal layer of example 1;
FIG. 3 is a cross-sectional electron scanning electron microscope image of the metallized ceramic of example 1 after brazing with the metal part to be welded;
FIG. 4 is a graph of seal strength after brazing of the metallized ceramic to the metal part to be welded in example 1;
FIG. 5 is a front side electron scanning electron microscope image of the sintered nickel metal layer of comparative example 1;
FIG. 6 is a cross-sectional electron scanning electron microscope image of the sintered nickel metal layer of comparative example 1;
FIG. 7 is a cross-sectional electron scanning electron microscope image of the metallized ceramic of comparative example 1 after brazing with the metal part to be welded;
FIG. 8 is a graph of seal strength after brazing of the metallized ceramic to the metal part to be welded in comparative example 1;
FIG. 9 is a front side electron scanning electron microscope image of the sintered nickel metal layer of example 2;
FIG. 10 is a cross-sectional electron scanning electron microscope image of the sintered nickel metal layer of example 2;
FIG. 11 is a front side electron scanning electron microscope image of the electroplated nickel metal layer of comparative example 2;
FIG. 12 is a cross-sectional electron scanning electron microscope image of the nickel-plated metal layer of comparative example 2;
FIG. 13 is a graph showing the seal strength after brazing the ceramic and the metal member to be welded in example 2 and comparative example 2;
FIG. 14 is a front side electron scanning electron microscope image of the sintered nickel metal layer of example 3;
FIG. 15 is a cross-sectional electron scanning electron microscope image of the sintered nickel metal layer in example 3.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention clearer, the present invention will be further described in detail with reference to examples. It should be understood that the examples described in this specification are for the purpose of illustrating the invention only and are not intended to limit the invention.
For simplicity, only a few numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
In the description herein, unless otherwise indicated, "above" and "below" are intended to include the present number, "one or more" means two or more, and "one or more" means two or more.
Embodiments of the first aspect of the present application provide a ceramic metallization paste comprising the following components: nickel powder, sintering aid and binder solution; wherein, the mass ratio of the nickel powder to the binder solution is (1-3): 1, a step of; the mass ratio of the nickel powder to the sintering aid is (80-98): 1, a step of; the sintering aid comprises copper metal powder and manganese metal powder or copper-manganese alloy powder;
when the particle diameter d of the nickel powder satisfies the following conditions: when d is more than or equal to 1 mu m and less than or equal to 5 mu m, the sintering aid also comprises nickel nano powder, wherein the particle size of the nickel nano powder is less than 1 mu m, and the mass percentage of each metal element in the sintering aid is as follows: mn is less than or equal to 4.5 percent and less than 68 percent; cu is more than or equal to 28.8 and less than 95 percent; ni is more than 0 and less than or equal to 10 percent;
when the particle diameter d of the nickel powder is smaller than 1 mu m, the mass percentage of each metal element in the sintering aid is as follows: mn is more than or equal to 5% and less than or equal to 68%; cu is more than or equal to 32% and less than or equal to 95%.
In the examples of the present application, when the particle diameter d of the nickel powder satisfies: when d is more than or equal to 1 mu m and less than or equal to 5 mu m, the sintering aid also comprises nickel nano powder, wherein the particle size of the nickel nano powder is less than 1 mu m, and the mass percentage of each metal element is as follows: mn is less than or equal to 4.5 percent and less than 68 percent; cu is more than or equal to 28.8 and less than 95 percent; ni is more than 0 and less than or equal to 10 percent; wherein, mn less than 4.5% or more than 68% by weight causes an increase in melting point thereof, which is unfavorable for fluidity and uniform distribution in the sintered nickel metal layer, and does not perform densification. When the weight percentage of Ni is more than 10%, two problems are brought about: 1. the melting point of the sintering aid is increased, so that the fluidity and uniform distribution in the sintered nickel metal layer are not facilitated, and densification is not achieved; 2. the addition of nano-sized nickel powders can result in excessive costs.
According to the embodiment of the present application, when the particle diameter d of the nickel powder satisfies: when d is more than or equal to 1 mu m and less than or equal to 5 mu m, copper-manganese alloy (formed by copper and manganese metal powder in a sintering aid or added in the form of copper-manganese alloy powder) is extremely easy to interact with a molybdenum-manganese metal layer with similar structure and composition in the high-temperature sintering process to form a complex multi-element alloy solid solution, and flows and migrates in a molybdenum-manganese metal porous structure to fill holes, so that the compactness of the molybdenum-manganese layer is enhanced. The nickel nano powder in the sintering aid exists in the form of nano nickel powder, and on one hand, the nano nickel powder has a melting point lower than that of the micron nickel powder or nickel components in the alloy are lower than that of the micron nickel powder, so that the contact area between the micron nickel powder particles can be increased, and the transition of the micron nickel powder to a nickel metal layer is promoted. On the other hand, copper metal and manganese metal are easy to interact with nickel metal to form complex alloy solid solution, so that flowing and spreading of the nickel metal on the surface of the molybdenum-manganese metal layer are enhanced, and a nickel metal layer with higher densification degree is formed.
In the embodiment of the application, when the particle size of the nickel powder is less than 1 μm, the sintering aid comprises the following metal elements in percentage by mass: mn is more than or equal to 5% and less than or equal to 68%; cu is more than or equal to 32% and less than or equal to 95%. Wherein, mn less than 5% or more than 68% by weight causes an increase in melting point thereof, which is unfavorable for fluidity and uniform distribution in the sintered nickel metal layer, and does not perform densification.
According to the embodiment of the application, when the particle size of the nickel powder is less than 1 mu m, the copper-manganese alloy is extremely easy to interact with a molybdenum-manganese metal layer with similar structure and composition to form a complex multi-element alloy solid solution in a high-temperature sintering process, and flows and migrates in a molybdenum-manganese metal porous structure to fill holes, so that the compactness of the molybdenum-manganese layer is enhanced. The raw material nickel powder is used as nano-scale nickel powder, on one hand, the melting point of the raw material nickel powder is lower than that of micron nickel powder or the nickel component in the alloy is lower than that of micron nickel powder, so that the contact area between micron nickel powder particles can be increased, the transition from micron nickel powder to a nickel metal layer is promoted, on the other hand, copper metal and manganese metal are easy to interact with nickel metal to form a complex alloy solid solution, and the flowing and spreading of nickel metal on the surface of a molybdenum-manganese metal layer are enhanced, so that a nickel metal layer with higher densification degree is formed.
In addition, in both cases, the nickel metal layer contains copper components, and during subsequent brazing with silver-copper solder, especially with copper metal pieces, the silver-copper solder is more favorable for flowing and spreading at the interface between the ceramic metallization layer and the metal pieces to be welded, and the welding strength is enhanced.
In embodiments of the present application, when the sintering aid includes copper metal powder and manganese metal powder, the particle size of both the copper metal powder and the manganese metal powder is no greater than 10 μm. When the particle size of the copper metal powder or the manganese metal powder is larger than 10 mu m, the specific gravity is increased, so that a stable slurry system is not easy to form, and the sedimentation phenomenon is easy to occur.
In embodiments of the present application, the sintering aid comprises a copper-manganese alloy powder having a particle size of no greater than 10 μm. When the particle size of the copper-manganese alloy powder is more than 10 mu m, the specific gravity is increased, which is unfavorable for forming a stable slurry system and is easy to generate sedimentation.
In embodiments of the present application, the binder solution comprises an aqueous binder solution or an oily binder solution. The aqueous binder solution or the oily binder solution has the functions of dispersing, thickening and the like on metal powder in a slurry system, and has the functions of bonding the metal powder on the surface of a molybdenum-manganese metal layer of ceramic and bonding between metal powder particles after screen printing and drying.
In the embodiment of the application, the aqueous binder solution comprises an aqueous binder and water, wherein the binder is a polymer with hydrophilic monomers and hydrophobic monomers, and the mass ratio of the hydrophilic monomers to the hydrophobic monomers is 1: (0.15-18); the mass ratio of the binder to the water is (0.2-1.5): 1. Its hydrophilic group interacts with ceramic metal powder, on the other hand, hydrophobic group prevents material agglomeration and sedimentation by its hydrophobicity. Therefore, when the mass ratio of the hydrophilic monomer to the hydrophobic monomer is too large or too small, the dispersibility thereof cannot be effectively exerted, resulting in unstable slurry and easy sedimentation.
The densified sintered nickel provided by the embodiment of the application can effectively reduce the use amount of noble metal solders such as silver, copper and the like, and the cost of raw materials of the solders can be saved by 90% at most. Taking a ceramic discharge tube product as an example, for a sintered nickel ceramic discharge tube (before densification) without densification and a sintered nickel ceramic discharge tube (after densification) subjected to densification by the technology, the welding strength of the ceramic discharge tube after densification can reach more than 130MPa under the use amount of silver-copper solder with the thickness of 5-10 microns, and the welding strength of the ceramic discharge tube before densification still can only reach about 100MPa under the use amount of silver-copper solder with the thickness of 100 microns.
In some embodiments, the hydrophobic monomer has the formula CH 2 ＝CR 1 R 2 Wherein R is 1 is-H or-CH 3 ；R 2 is-CN, -C 6 H 5 、-COOR 3 Wherein R is 3 Is alkyl, cycloalkyl or aryl;
in some embodiments, the hydrophilic monomer has the structural formula: CHR (CHR) 4 ＝CR 5 R 6 Wherein R is 4 And R is 5 Are all-H or-CH 3 or-COOM; r is R 6 is-COOM, -CH 2 COOM、-COO(CH 2 ) 6 SO 3 M、-CONH 2 、-CONHR 7 Wherein R is 7 Is alkyl or cycloalkyl; m is any one of H element or metal element related in ceramic metal powder.
In an embodiment of the present application, the oily binder solution includes an oily binder and an organic solvent, wherein the binder includes ethyl cellulose or nitrocellulose; the organic solvent is selected from terpineol, diethylene glycol ether acetate, tributyl citrate or tributyl phthalate; the concentration of the oily binder solution is 0.024-0.054 g/mL, for example, 60-80 g binder is obtained by dissolving in 1500-2500 mL solvent.
A second aspect of embodiments of the present application provides a sintered nickel process comprising the steps of:
stirring and mixing the nickel powder, the sintering aid and the binder solution at the temperature of 1-90 ℃ to obtain nickel metallization slurry, wherein the viscosity of the nickel metallization slurry is 2500-8000 mPa.s;
and coating the obtained nickel metallization slurry on the surface of the molybdenum-manganese metallized ceramic part, and then drying and sintering to obtain the nickel metal layer.
In the embodiment of the application, the viscosity of the nickel metallization slurry is controlled to 2500-8000 mPa.s by controlling the types and the addition amount of the binder, the addition amount, the size, the stirring and mixing temperature and the like of the metal powder. When the viscosity is lower than 2500 mPa.s, the slurry is easy to settle and easy to overflow during coating; when the viscosity is higher than 8000 mPa.s, the fluidity of the slurry becomes poor, the slurry cannot be knife coated, and the coating is easy to crack.
The slurry preparation process according to the embodiment of the application can only use water as a solvent, the water is colorless and odorless, the physical and mental health of production workers cannot be damaged in the drying process, the environment is protected, and the solvent cost is reduced.
The aqueous slurry according to the embodiment of the application can be prepared and printed at normal temperature, and the energy consumption cost is reduced.
The method for sintering nickel on the ceramic surface provided by the embodiment of the application enhances the compactness of the sintered nickel, thereby enhancing the wettability of the solder on the ceramic metal layer and effectively preventing the solder from diffusing and migrating to the loose and porous molybdenum-manganese metal layer during high-temperature brazing.
The ceramic surface sintering nickel technology provided by the embodiment of the application is very environment-friendly, and solves the problem of electroplating wastewater pollution existing in the nickel coating process.
In the embodiment of the application, the drying temperature is 5-80 ℃ and the drying time is 5-120min. At the temperature, the drying can be carried out after the drying time is less than 5min, and the drying effect is not further improved after the drying time exceeds 120min, so that the energy consumption is increased and the production efficiency is reduced.
In the examples of the present application, the sintering temperature is 800 to 1100 ℃; the sintering time is 5-30 min. The main components in the ceramic metalized slurry are chemically changed at 800-1100 ℃ and the sintering time is 5-30 min. The above is to make the chemical change more sufficient, and the time longer than 30min has no obvious benefit on the metallization effect, but can increase the energy consumption and reduce the production efficiency.
The third aspect of the embodiment of the application also provides a metallized ceramic part, which comprises a molybdenum-manganese metallized ceramic part and a nickel metal layer prepared by the nickel sintering process, wherein the thickness of the nickel metal layer is 0.5-15 mu m.
The density of the nickel metal layer in the metallized ceramic part is high, so that the welding strength and the air tightness are enhanced, the wettability of the solder on the ceramic metal layer is enhanced, and the diffusion and migration of the solder to the loose and porous molybdenum-manganese metal layer during high-temperature brazing are effectively prevented.
Examples
The following examples more particularly describe the disclosure of the present application, which are intended as illustrative only, since numerous modifications and variations within the scope of the disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
In order to reduce the influence of the molybdenum-manganese layer on the sintered nickel, the experiment adopts ceramic tubes which are subjected to molybdenum-manganese metallization by enterprises to carry out the process study of the sintered nickel. A certain amount of binder is weighed and dissolved in water, and stirred at a certain temperature until all the binder is dissolved into transparent and viscous solution. Then, a certain amount of nickel powder is weighed and mixed with the binder solution, a certain amount of thickener is added, and then ball milling and mixing are carried out for a certain time in a ball mill at a certain temperature, so as to obtain nickel metal slurry with uniform components. Then, a 250-mesh silk screen is adopted to carry out printing coating on the nickel metal slurry, the nickel metal slurry is coated on the surface of a molybdenum-manganese metallized layer of a ceramic discharge tube, the ceramic discharge tube is dried, organic matters such as a binder and the like are removed in a hydrogen atmosphere at a high temperature of about 1000 ℃, and then a ceramic product after sintering nickel metallization is obtained, and the influence of constant temperature time of 5min,10min and 15min on sintering nickel is examined respectively. The microscopic morphology of the nickel metal layer is observed by adopting an electronic scanning electron microscope.
Example 1
The embodiment provides ceramic surface nickel metallization slurry, which comprises the following raw material components: the sintering device comprises nickel metal powder, a sintering aid and a binder solution, wherein the mass ratio of the nickel metal powder to the binder solution is 1.5:1, the mass ratio of the nickel metal powder to the sintering aid is 90:1, and the particle size of the nickel metal powder is 5 microns; the binder solution comprises a binder and water, wherein the mass ratio of the binder to the water is 1:1, and the mass ratio of hydrophilic monomers to hydrophobic monomers in the binder is 1:10, wherein the hydrophobic monomer is acrylonitrile, the hydrophilic monomer is acrylic acid salt, and the acrylic acid nitrile and acrylic acid salt are copolymerized in an aqueous phase to prepare a binder; the sintering aid is composed of copper powder, manganese powder and nickel nano powder, wherein the mass percentage of Mn is 4.8%, cu is 91.2%, ni is 4%, the particle sizes of the copper powder and the manganese powder are about 5 microns, and the particle size of the nickel nano powder is about 200 nm.
The preparation method for preparing the nickel metallization slurry by using the raw materials comprises the following steps:
(1) Mixing nickel powder and sintering aid according to the raw material components, adding binder solution, and stirring at normal temperature to obtain nickel metal slurry; the viscosity of the ceramic metallization slurry is 3460 mPa.s.
(2) And (3) coating the obtained nickel-metalized slurry on the surface of the molybdenum-manganese metal layer of the ceramic piece in a screen printing mode, wherein a screen is 200 meshes, and then drying and sintering to obtain the nickel-metalized ceramic piece. In the step (2), the drying temperature is 60 ℃ and the drying time is 40 minutes. The sintering temperature in the step (2) is 1000 ℃, and the heat preservation time is 30 minutes. The ceramic piece is a ceramic ring with the diameter of 8mm, the wall thickness of 0.8mm and the height of 10mm, and the nickel metallization is treated on the surface of the molybdenum-manganese metallization layer on the end face of the ceramic ring.
The metallized ceramic and the metal to be welded (oxygen-free copper) are used for brazing, and the method comprises the following steps:
and (3) using a silver-copper solder sheet with the thickness of 0.1mm as a solder, placing the solder between the metallized ceramic piece and the metal piece to be soldered, and performing high-temperature soldering at the temperature of about 850 ℃ in vacuum or inert atmosphere or reducing atmosphere to realize packaging.
The sealing tensile strength is tested by adopting a microcomputer control universal tester according to SJ/T3326-2016 standard; the seal tightness was tested using a helium mass spectrometer leak detector according to the SJ/T11583-2016 standard.
Fig. 1 is a front-side sem image (a low-power image, b high-power image) of the sintered nickel metal layer in this embodiment, and it can be derived from fig. 1: the nickel metal layer is very dense.
Fig. 2 is a cross-sectional electron scanning electron microscope (sem) image of the sintered nickel metal layer in this embodiment (the region between the two dotted lines is the sintered nickel metal layer), and it can be derived from fig. 2: the thickness of the nickel metal layer is about 10 mu m, and the thickness is very uniform;
FIG. 3 is a cross-sectional electron scanning electron microscope (silver brazing material layer in the region between the first and second dotted lines from top to bottom; sintered nickel metal layer in the region between the second and third dotted lines from top to bottom; molybdenum-manganese-metallized Al in the region below the third dotted line from top to bottom) of a ceramic metal to be soldered in the present embodiment 2 O 3 Ceramic matrix), from fig. 3, it can be derived: the thicknesses of the nickel metal layer and the silver brazing material layer are about 10 mu m, and the thicknesses are very uniform;
FIG. 4 is a graph showing the seal strength after brazing the metallized ceramic to the metal part to be welded in this example, as can be seen from FIG. 4: the sealing tensile strength is 135MPa;
further, the sealing tightness test results show that: sealing air tightness<5.0×10 -12 Pa·m 3 /s。
Comparative example 1
This comparative example is different from example 1 in that the ceramic nickel-plated slurry provided in this comparative example does not contain a sintering aid, and the viscosity of the ceramic-plated slurry thus obtained is 3250mpa·s, otherwise the same as in example 1.
The metallized ceramic and the metal to be welded (oxygen-free copper) are used for brazing, and the method comprises the following steps:
and (3) using a silver-copper solder sheet with the thickness of 0.1mm as a solder, placing the solder between the metallized ceramic piece and the metal piece to be soldered, and performing high-temperature soldering at the temperature of about 850 ℃ in vacuum or inert atmosphere or reducing atmosphere to realize packaging.
The sealing tensile strength is tested by adopting a microcomputer control universal tester according to SJ/T3326-2016 standard; the seal tightness was tested using a helium mass spectrometer leak detector according to the SJ/T11583-2016 standard.
Fig. 5 is a front side electron scanning electron microscope image of the sintered nickel metal layer in this comparative example, and it can be derived from fig. 5: the nickel metal layer is provided with a plurality of holes, is not compact, and is easy to cause migration and diffusion of silver-copper solder to the molybdenum-manganese metal layer through the holes, so that the sealing strength is reduced;
fig. 6 is a cross-sectional electron scanning electron microscope (sem) image of the sintered nickel metal layer in this comparative example (the region between the two dotted lines is the sintered nickel metal layer), and it can be derived from fig. 6: the thickness of the nickel metal layer is about 10 mu m, and the thickness is very uniform;
fig. 7 is a cross-sectional electron scanning electron microscope image of the comparative example after brazing the metallized ceramic and the metal piece to be welded (the area between the first and second dotted lines from top to bottom is a silver brazing material layer; the area between the second and third dotted lines from top to bottom is a sintered nickel metal layer), and it can be derived from fig. 7: the thickness of the silver brazing material layer is only about 40 mu m, and the initial thickness of the used silver brazing material sheet is 100 mu m, which shows that part of silver brazing material migrates and diffuses to the molybdenum manganese metal layer through the holes;
FIG. 8 is a graph of the seal strength after brazing the metallized ceramic to the metal part to be welded in this comparative example, as can be derived from FIG. 8: the sealing tensile strength is 96MPa, which indicates that the non-compact sintered nickel layer can reduce the sealing strength; in addition, the sealing tightness is reduced, and the sealing tightness test result shows that: sealing air tightness<4.3×10 -11 Pa·m 3 /s。
From the comparative analysis of the results of example 1 and comparative example 1, the welding strength of the sintered nickel ceramic discharge tube (before densification) without densification and the sintered nickel ceramic discharge tube (after densification) with densification by the present technique was increased to 130MPa or more by brazing the ceramic discharge tube with a silver-copper solder of 5 to 10 μm thickness, and the welding strength of the sintered nickel ceramic discharge tube before densification was increased to about 100MPa by brazing with a silver-copper solder of 100 μm thickness.
Example 2
The embodiment provides ceramic surface nickel metallization slurry, which comprises the following raw material components: the sintering device comprises nickel metal powder, a sintering aid and a binder solution, wherein the mass ratio of the nickel metal powder to the binder solution is 1.2:1, the mass ratio of the nickel metal powder to the sintering aid is 95:1, and the particle size of the nickel metal powder is 600nm; the binder solution comprises binder ethyl cellulose and terpineol solvent, 70g ethyl cellulose is dissolved in 2000ml terpineol; the sintering aid is copper-manganese alloy powder, wherein the mass percentage of Mn is 30%, the balance is Cu, and the particle size of the copper-manganese alloy powder is 1 micron.
The preparation method for preparing the nickel metallization slurry by using the raw materials comprises the following steps:
(1) Mixing nickel powder and sintering aid according to the raw material components, adding binder solution, and stirring at normal temperature to obtain nickel metal slurry; the viscosity of the ceramic metallization slurry is 5890 mPa.s.
(2) And (3) coating the obtained nickel-metalized slurry on the surface of the molybdenum-manganese metal layer of the ceramic piece in a screen printing mode, wherein a screen is 150 meshes, and then drying and sintering are carried out to obtain the nickel-metalized ceramic piece. In the step (2), the drying temperature is 70 ℃ and the drying time is 20 minutes. The sintering temperature in the step (2) is 950 ℃, and the heat preservation time is 10 minutes. The ceramic piece is a ceramic ring with the diameter of 8mm, the wall thickness of 0.8mm and the height of 10mm, and the nickel metallization is treated on the surface of the molybdenum-manganese metallization layer on the end face of the ceramic ring.
The metallized ceramic and the metal to be welded (oxygen-free copper) are used for brazing, and the method comprises the following steps:
and (3) using a silver-copper solder sheet with the thickness of 0.1mm as a solder, placing the solder between the metallized ceramic piece and the metal piece to be soldered, and performing high-temperature soldering at the temperature of about 850 ℃ in vacuum or inert atmosphere or reducing atmosphere to realize packaging.
The sealing tensile strength is tested by adopting a microcomputer control universal tester according to SJ/T3326-2016 standard; the seal tightness was tested using a helium mass spectrometer leak detector according to the SJ/T11583-2016 standard.
FIG. 9 is a front-side electron Scanning Electron Microscope (SEM) image of the sintered nickel metal layer of the present example, which shows that the nickel metal layer is very dense;
fig. 10 is a sectional electron scanning electron microscope (sem) image of the sintered nickel metal layer in this example (the region between the two dotted lines is the sintered nickel metal layer), and it is apparent that the thickness of the nickel metal layer is about 4 μm and is very uniform.
Comparative example 2
Electroplating nickel: and (3) putting the ceramic piece after molybdenum-manganese metallization into electroplating solution containing nickel ions, reducing and depositing the nickel ions on the surface of the molybdenum-manganese metal according to a certain current, filtering, washing and drying to obtain the ceramic piece after nickel metallization. The ceramic piece is a ceramic ring with the diameter of 8mm, the wall thickness of 0.8mm and the height of 10 mm.
Solder packaging is the same as in embodiment 2: and (3) using a silver-copper solder sheet with the thickness of 0.1mm as a solder, placing the solder between the metallized ceramic piece and the metal piece to be soldered, and performing high-temperature soldering at the temperature of about 850 ℃ in vacuum or inert atmosphere or reducing atmosphere to realize packaging.
FIG. 11 is a front electron Scanning Electron Microscope (SEM) image of the electroplated nickel metal layer of comparative example 2, which shows that a layer of very uniform nano nickel particles is deposited on the surface of the molybdenum-manganese metal layer by electroplating, and the particles are very dense.
FIG. 12 is a sectional electron Scanning Electron Microscope (SEM) image of the electroplated nickel metal layer of comparative example 2 (the region between the two dotted lines is a sintered nickel metal layer), and it is apparent that the nickel metal layer has a thickness of about 2 μm and is very uniform, and the nickel metal layer is very thin and dense in the nickel metal layer by electroplating.
Fig. 13 is a graph showing the comparison of the seal strength after brazing the ceramic and the metal member to be welded in example 2 and comparative example 2, and it is understood that the seal tensile strength of each of example 2 and comparative example 2 is about 130 MPa.
In addition, the sealing air tightness test result shows that: example 2 sealing gas tightness<2.1×10 -12 Pa·m 3 S; sealing gas tightness of comparative example 2<3.4×10 -12 Pa·m 3 /s。
From the comparison analysis of the results of the embodiment case 2 and the comparison case 2, taking the ceramic discharge tube product as an example, after densification treatment is carried out on the sintered nickel structure, the tensile strength and the sealing air tightness of the product after the product is sealed with the metal to be welded completely reach the level of electroplated nickel, which shows that the product can effectively prevent the diffusion and migration of the solder to the loose porous molybdenum-manganese metal layer during high-temperature brazing.
Example 3
The embodiment provides ceramic surface nickel metallization slurry, which comprises the following raw material components: the sintering device comprises nickel metal powder, a sintering aid and a binder solution, wherein the mass ratio of the nickel metal powder to the binder solution is 2.1:1, the mass ratio of the nickel metal powder to the sintering aid is 85:1, and the particle size of the nickel metal powder is 2 mu m; the binder solution comprises a binder and water, wherein the mass ratio of the binder to the water is 1.4:1, and the mass ratio of hydrophilic monomers to hydrophobic monomers in the binder is 1:5, wherein the hydrophobic monomer is styrene, the hydrophilic monomer is methacrylic acid, and the styrene and the methacrylic acid are copolymerized in an aqueous phase to prepare the adhesive; the sintering aid is copper-manganese alloy powder and nickel nano powder, wherein the mass percentage of Mn is 49%, cu is 49%, ni is 2%, the particle size of the copper-manganese-nickel alloy powder is 1 micron, and the particle size of the nickel nano powder is about 600 nm.
The preparation method for preparing the nickel metallization slurry by using the raw materials comprises the following steps:
(1) Mixing nickel powder and sintering aid according to the raw material components, adding binder solution, and stirring at normal temperature to obtain nickel metal slurry; the viscosity of the ceramic metallization slurry is 3280 mPa.s.
(2) And (3) coating the obtained nickel-metalized slurry on the surface of the molybdenum-manganese metal layer of the ceramic piece in a screen printing mode, wherein a screen is 200 meshes, and then drying and sintering to obtain the nickel-metalized ceramic piece. In the step (2), the drying temperature is 40 ℃ and the drying time is 80 minutes. The sintering temperature in the step (2) is 9800 ℃, and the heat preservation time is 30 minutes. The ceramic piece is a ceramic ring with the diameter of 8mm, the wall thickness of 0.8mm and the height of 10mm, and the nickel metallization is treated on the surface of the molybdenum-manganese metallization layer on the end face of the ceramic ring.
Fig. 14 is a front side electron scanning electron microscope image of the sintered nickel metal layer in this embodiment, as can be derived from fig. 14: the nickel metal layer is very dense;
fig. 15 is a sectional electron scanning electron microscope (sem) image of the sintered nickel metal layer in this embodiment (the region between two dotted lines is the sintered nickel metal layer), and it can be derived from fig. 15: the nickel metal layer has a thickness of about 12 μm and is very uniform.
The seal strength test result of example 3 showed that the seal tensile strength was 131MPa. In addition, it is shown from the sealing air tightness test result that the sealing air tightness is<4.2×10 -12 Pa·m 3 /s。
While the present application has been described with reference to a preferred embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the present application, and in particular, the technical features mentioned in the various embodiments may be combined in any manner as long as there is no structural conflict. The present application is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.
Claims (10)
1. A ceramic metallizing slurry comprising the following components: nickel powder, sintering aid and binder solution; wherein, the mass ratio of the nickel powder to the binder solution is (1-3): 1, a step of; the mass ratio of the nickel powder to the sintering aid is (80-98): 1, a step of; the sintering aid comprises copper metal powder and manganese metal powder or copper-manganese alloy powder;
when the particle diameter d of the nickel powder satisfies the following conditions: when d is more than or equal to 1 mu m and less than or equal to 5 mu m, the sintering aid also comprises nickel nano powder, wherein the particle size of the nickel nano powder is less than 1 mu m, and the mass percentage of each metal element in the sintering aid is as follows: mn is less than or equal to 4.5 percent and less than 68 percent; cu is more than or equal to 28.8 and less than 95 percent; ni is more than 0 and less than or equal to 10 percent;
when the particle diameter d of the nickel powder is smaller than 1 mu m, the mass percentage of each metal element in the sintering aid is as follows: mn is more than or equal to 5% and less than or equal to 68%; cu is more than or equal to 32% and less than or equal to 95%.
2. The ceramic metallization paste of claim 1, wherein when the sintering aid comprises copper metal powder and manganese metal powder, the particle size of both copper metal powder and manganese metal powder is no greater than 10 μm.
3. The ceramic metallization paste of claim 1, wherein when the sintering aid comprises a copper-manganese alloy powder, the particle size of the copper-manganese alloy powder is no greater than 10 μm.
4. The ceramic metallization paste of claim 1, wherein the binder solution comprises an aqueous binder solution or an oily binder solution.
5. The ceramic metallization paste of claim 4, wherein the aqueous binder solution comprises an aqueous binder and water, wherein the binder is a polymer with both hydrophilic monomers and hydrophobic monomers, and the mass ratio of the hydrophilic monomers to the hydrophobic monomers is 1: (0.15-18); the mass ratio of the binder to the water is (0.2-1.5): 1.
6. The ceramic metallization paste of claim 4, wherein the oily binder solution comprises an oily binder and an organic solvent, wherein the binder comprises ethyl cellulose or nitrocellulose; the organic solvent is selected from terpineol, diethylene glycol ether acetate, tributyl citrate or tributyl phthalate; the concentration of the oily binder solution is 0.024-0.054 g/mL.
7. A process for sintering nickel, comprising the steps of:
mixing the nickel powder according to any one of claims 1-6, a sintering aid and a binder solution at 1-90 ℃ under stirring to obtain a nickel-metallized slurry, wherein the viscosity of the nickel-metallized slurry is 2500-8000 mPa-s;
and coating the obtained nickel metallization slurry on the surface of the molybdenum-manganese metallized ceramic part, and then drying and sintering to obtain the nickel metal layer.
8. The process for sintering nickel according to claim 7, wherein the drying temperature is 5-80 ℃ and the drying time is 5-120min.
9. The nickel sintering process according to claim 7, wherein the sintering temperature is 800-1100 ℃; the sintering time is 5-30 min.
10. A metallized ceramic comprising a molybdenum manganese metallized ceramic and a nickel metal layer produced by the sintered nickel process of any one of claims 7-9, said nickel metal layer having a thickness of 0.5-15 μm.
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| CN202311249868.0A Pending CN117466670A (en) | 2023-09-26 | 2023-09-26 | Nickel metal slurry, nickel sintering process and metallized ceramic part |
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