CN1027797C - Oxidation-resistant active metal solder capable of welding ceramics - Google Patents
Oxidation-resistant active metal solder capable of welding ceramics Download PDFInfo
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- CN1027797C CN1027797C CN 92106103 CN92106103A CN1027797C CN 1027797 C CN1027797 C CN 1027797C CN 92106103 CN92106103 CN 92106103 CN 92106103 A CN92106103 A CN 92106103A CN 1027797 C CN1027797 C CN 1027797C
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- Prior art keywords
- solder
- rare earth
- oxidation
- ceramic
- metal
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 39
- 239000000919 ceramic Substances 0.000 title claims abstract description 19
- 238000003466 welding Methods 0.000 title claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 title abstract description 16
- 239000002184 metal Substances 0.000 title abstract description 16
- 238000007254 oxidation reaction Methods 0.000 title abstract description 14
- 230000003647 oxidation Effects 0.000 title abstract description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- -1 rare earth compound Chemical class 0.000 claims abstract description 3
- 238000005476 soldering Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 230000003064 anti-oxidating effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000005219 brazing Methods 0.000 abstract description 6
- 239000007769 metal material Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 3
- 230000000996 additive effect Effects 0.000 abstract 3
- 239000002131 composite material Substances 0.000 abstract 2
- 239000000945 filler Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 240000006409 Acacia auriculiformis Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910002064 alloy oxide Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 1
- 239000011225 non-oxide ceramic Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- Ceramic Products (AREA)
Abstract
The invention belongs to the technical field of welding, and provides an oxidation-resistant active metal solder capable of welding ceramics, which mainly contains Cu, Ag and Ti, and is characterized in that: adding an antioxidant additive and a composite rare earth additive into the Cu-Ag-Ti active solder, wherein the solder comprises the following components in percentage by atom:
rare earth additive Cu as antioxidant additive of Ag and Ti
5-601-102-100-0.8 of the balance
Wherein the antioxidant additive refers to Al or Cr, and the rare earth additive refers to Ce or a composite rare earth compound mainly containing Ce. The invention has enough high temperature oxidation resistance, is particularly suitable for ceramic-to-ceramic brazing which can not be finished by common metal brazing filler metal to form ceramic-to-metal brazing, and is also suitable for common metal material brazing.
Description
The invention belongs to welding technology field, specifically just provided a kind of enough oxidation-resistance properties that has, be suitable for the pottery that the common metal solder can't finish and the solder of ceramic soldering or pottery and solder bonding metal.
Since the nearly period, because the joint efforts of countries in the world scientific circles and industrial quarters make traditional ceramic material property that revolutionary variation take place, fine ceramics develops just rapidly as an emerging branch of industry, and its product progresses into the practicability stage.Yet because some intrinsic shortcomings of ceramic material itself, levy fragility as wood, intensity dispersion and unworkability or the like still were difficult to overcome in a short time, make this new material with great potential before the application that enlarges it, must at first solve it and other material, it at first is the connectivity problem of metal material, in the product that many ceramic materials that entered practicability are at present made, as microwave electronic device, the electrode of ceramic capacitor and wave filter, large quantities of electrovacuum elements such as vacuum insulation seal, vacuum electrode lead-in wire etc., the pottery cutting tool, comprise diamond cut instrument or the like, metal is one of technological core during these technology-intensive products are made with ceramic the connection reliably.In known metal and the ceramic interconnection technique, organic bonding and inorganic adhesive, because its production cost is low, simple to operate and wide adaptability and application widely, but the former major defect is that temperature raises, bonded joint will lose efficacy rapidly, and that the latter's shortcoming is a bonding strength is very low, and joint is very unreliable.Diffusion welding (DW), high temperature insostatic pressing (HIP) weldering, electron beam or extraordinary solder technology such as laser fusion welding and friction welding (FW) can be produced in conjunction with firm metal/ceramic joint, but it is very high that their common shortcomings are production costs, and concerning each technology, the scope of application is rather narrow.Soldering is the higher method of a kind of relative productivity indirectly, but because its requirement is carried out metalized in advance to ceramic surface, so increased production process and production cost.At present in many metals and the ceramic method that is connected, with the direct soldering tech of reactive metal, because productivity ratio height, wide adaptability connects reliable and multiple advantage such as production cost is low and have competitiveness most, the core of this technology be can be on pottery the development of the wetting and active metallic soldering material of adhering.EP0104623(1983) a kind of auri or palladium based active solder are provided, these active solders are enough to keep a lower oxidation rate owing to contain noble metal, but because the cost of raw material is too high-leveled and difficult to obtain general application, EP0135603(1983) provide a kind of money base active solder, GB2066291A(1981) provide a kind of copper-based active solder, the spy opens clear 62-16896(1987) a kind of copper-Yin-Ni-Ti sandwich-type active metallic soldering material, the solder that the production cost of this three classes solder all provides well below document be provided.But owing to no matter be cupric oxide, titanium oxide or nickel oxide; it all is the oxide-film of non-protective; their common drawback is at high temperature to heat; active solder is rapid oxidation, so, if with the metal/ceramic joint of these solder brazings at oxidizing atmosphere (as atmosphere) be higher than under the uniform temperature of room temperature and work; joint will lose efficacy rapidly owing to the oxidation of solder; on this meaning, present urgent need will develop cheaply a kind of, but the practical active solder of sludge proof.
The object of the present invention is to provide a kind of active metallic soldering material of resistance to oxidation type, under certain condition can be directly wetting at multiple ceramic surface, sprawl and solidify the back and pottery fuse securely.
But the invention provides a kind of anti-oxidation active metallic material of welding ceramics, mainly contain Cu, Ag, Ti, it is characterized in that: add antioxidant and compound interpolation rare earth addition in above-mentioned Cu-Ag-Ti active solder, the percentage composition of solder is (atomic percent):
Ag Ti antioxidant rare earth addition Cu
5-60 1-10 2-10 0-0.8 surplus
Wherein antioxidant refers to Al or Cr, and rare earth addition refers to Ce or based on the compound rare-earth compound of Ce.
In the present invention, the effect of active element is to make solder can be on pottery wetting and adhere to.The effect of nonactive element be improve and the control solder on pottery wetability and with the bonding strength of pottery, antioxidant is used to improve solder oxidation resistance at high temperature, the effect of rare earth addition is the interface binding power that strengthens alloy oxide film and parent metal, also can not add.
Solder prescription provided by the invention can carry out alloying with pyrometallurgy or Physical Metallurgy, can select one or more mechanism's processing after the alloying, solder is made suitable shape, as solder wire, solder powder or solder sheet etc.
Compare with original technology, solder provided by the invention, the ability of resistance to high temperature oxidation strengthens greatly, contains the metal solder of Cu for this class, and general oxidation behavior is all obeyed the second-degree parabola law
△W
2＝Kt
△ W is the oxidation weight gain of unit are in the formula, K is a work parabola constant, t is an oxidization time, test as a comparison, relatively by Cu-5Ti-57Ag that EP0135603 provided and will begin Cu-5Ti-55Ag-5Ni and the Cu-5Ti-54Ag-4.5Ag-0.5Ce provided by the invention that 62-16896 provides, oxidation in 600 ℃ of following air, its parabola constant K is respectively 6.29 * 10
-5Mg
2/ cm
4S, 6.05 * 10
-5Mg
2/ cm
4S and 3.18 * 10
-5Mg
2/ cm
2About S, active solder promptly provided by the invention are doubled the oxidation drag.Solder provided by the invention can be at multiple pottery, comprise oxide ceramics (aluminium oxide, quartz, mullite, zirconia etc.), non-oxide ceramics (diamond, graphite, silicon nitride, Sialon, carborundum etc.) well wetting and adhesion effect directly takes place on the surface, and be equally applicable to the soldering of metal and alloy, embodiment is described in detail in detail below:
Embodiment 1
The alloy of preparation Cu-5Ti-54Ag-5Cr under the Ar gas shiled, carries out melting with tungsten arc.It is even to adopt electromagnetic field to stir to guarantee alloy composition in the fusion process, and the alloy after the melting can cold rolling one by one one-tenth solder sheet through middle vacuum annealing.
Silicon nitride ceramics, the surface is carefully cleaned with ultrasonic wave in acetone after careful the grinding, then, places in the vacuum brazing furnace, gets suitable solder sheet surface grinding and clean to be placed on the ceramic surface.The sealing furnace chamber also vacuumizes, when vacuum reaches 1 * 10
-5Behind the Torr, gently be warming up to 880 ℃, be incubated 5 minutes, slowly pit furnace is as cold as room temperature then.Solder is wetting good at ceramic surface, and is connected firmly.
Embodiment 2
Preparation Cu-5Ti-54Ag-4.5Al-0.5Ce alloy is tested with method same among the embodiment 1, and pottery is selected Sialon for use, found that, solder is wetting good at ceramic surface, and is connected firmly with pottery.
Claims (2)
1, a kind of anti-oxidation active metallic soldering material for welding ceramics, mainly contain Cu, Ag, Ti, it is characterized in that: add antioxidant and compound interpolation rare earth addition in above-mentioned Cu-Ag-Ti active solder, the percentage composition of solder is (atomic percent):
Ag Ti antioxidant rare earth addition Cu
5-60 1-10 2-10 0-0.8 surplus
Wherein antioxidant refers to Al or Cr, and rare earth addition refers to Ce or based on the compound rare-earth compound of Ce.
2, by the described anti-oxidation active metallic soldering material of claim 1, what it is characterized in that solder is shaped as silk, powder or sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92106103 CN1027797C (en) | 1992-03-25 | 1992-03-25 | Oxidation-resistant active metal solder capable of welding ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92106103 CN1027797C (en) | 1992-03-25 | 1992-03-25 | Oxidation-resistant active metal solder capable of welding ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1076648A CN1076648A (en) | 1993-09-29 |
| CN1027797C true CN1027797C (en) | 1995-03-08 |
Family
ID=4941797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92106103 Expired - Fee Related CN1027797C (en) | 1992-03-25 | 1992-03-25 | Oxidation-resistant active metal solder capable of welding ceramics |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1027797C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052674C (en) * | 1995-09-27 | 2000-05-24 | 中国科学院金属研究所 | Tin-base active flux for soldering ceramic under coarse vacuum condition |
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|---|---|---|---|---|
| EP2469562A1 (en) * | 2010-12-22 | 2012-06-27 | ABB Technology AG | Interrupter insert for a circuit breaker arrangement |
| FR3014000A1 (en) * | 2013-11-29 | 2015-06-05 | Diamonde | METHOD FOR MANUFACTURING AND REPAIRING A CUTTING TOOL |
| CN105948779A (en) * | 2016-04-25 | 2016-09-21 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of silicon nitride ceramic/metal composite plate |
| DE102017114893B4 (en) * | 2017-07-04 | 2023-11-23 | Rogers Germany Gmbh | Soldering material for active soldering and method for active soldering |
| CN110202294A (en) * | 2019-05-09 | 2019-09-06 | 华侨大学 | A kind of Sn-Cu-V solder for low temperature brazing diamond |
| CN112059470A (en) * | 2020-09-08 | 2020-12-11 | 中物院成都科学技术发展中心 | Active brazing filler metal for brazing titanate microwave dielectric ceramic and metal and preparation method thereof |
| CN113528884B (en) * | 2021-07-21 | 2021-12-28 | 广东省科学院中乌焊接研究所 | Copper-based interlayer alloy and preparation method thereof, ceramic and oxygen-free copper composite connecting piece and welding method thereof |
| CN117532198B (en) * | 2024-01-09 | 2024-03-22 | 河北省科学院能源研究所 | Ag-Cu-based active solder and production method and application thereof |
-
1992
- 1992-03-25 CN CN 92106103 patent/CN1027797C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052674C (en) * | 1995-09-27 | 2000-05-24 | 中国科学院金属研究所 | Tin-base active flux for soldering ceramic under coarse vacuum condition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1076648A (en) | 1993-09-29 |
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