CN1037825C - Copper-base solder-silver substituted solder for electrical vacuum with low melting point, low vapour pressure and ductility - Google Patents
Copper-base solder-silver substituted solder for electrical vacuum with low melting point, low vapour pressure and ductility Download PDFInfo
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- CN1037825C CN1037825C CN95111020A CN95111020A CN1037825C CN 1037825 C CN1037825 C CN 1037825C CN 95111020 A CN95111020 A CN 95111020A CN 95111020 A CN95111020 A CN 95111020A CN 1037825 C CN1037825 C CN 1037825C
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Abstract
The present invention relates to a copper base brazing solder with low melting point, low vapor pressure and low ductility, which is used for substituting for silver solders in an electrical vacuum comprises has the main components of Cu, Ag, Sn and In. The brazing temperature of the solder is corresponding to that of AgCu28 to the wetting property and gap filling property of oxygen-free copper, kovar and nickel, and the cost of the solder is only about one third of that of AgCu28. The solder can substitute for AgCu28 and be used for the sealing of ceramic pipes and in other occasions for brazing copper, oxygen-free copper, nickel, kovar and metallized ceramics.
Description
The present invention relates to the solder, particularly copper base solder that use in the electrovacuum field.
Soldering tech is widely used in the production of electron tube, because the requirement of electrovacuum, the metal solder of filling during soldering is except having appropriate melting point, good wetting property and joint filling, outside the performance that general solder such as certain intensity should have, also require it to have low vapour pressure.The electrovacuum of China's standard brand has DHLAgCu28 with silver solder, DHLAgCu50 etc., wherein DH-LAgCu28 consumption maximum at present.Yet silver is a kind of noble metal, not only costs an arm and a leg, and resource-constrained, and its use will be limited by the strictness of country.Therefore people are constantly seeking new no silver or low-silver solder to replace silver solder.
In numerous silver-substituted solder patents, one class is the Cu-Ag base low-silver solder that contains Cd or contain Zn, though this class solder function admirable, but owing to contain the Cd of high vapour pressure, elements such as Zn, and can not be used for the electrovacuum field, while Cd, Zn major part in brazing process has gasified, and fills the air in air, and human body key health is also had bigger damaging effect.Another kind of silver-substituted solder is that this class cored solder is specially adapted to brazed copper and copper alloy by the Cu-P base system row silver-substituted solder of flash set technology preparation, but owing to contain a large amount of P elements, and can not be used for soldering nickel, can cut down metallized ceramic, electrovacuum common used materials such as stainless steel.In the patent of invention of four silver-substituted solders announcing as China, have the binomial solder to contain Zn, binomial contains P in addition, and they all fail to obtain to use in the electrovacuum field.
Can be used for the electrovacuum field relatively low solder of silver content at present and mainly contain Cu-Ag base or the Ag-Cu base solder that contains Sn or contain Si.The low silver-colored electrovacuum solder of Cu-Ag base of a kind of Si of containing has been described as US Patent No 4,416,853, its steam forces down, and is good to the nickel wetability, the soldering strength height, but for making its fusing point lower (＜800 ℃), it need contain the Si (about 7wt%) of a great deal of, thereby it is unsuitable for containing H
2Weld in the atmosphere, and because high si content, this class solder is highly brittle, and almost can not be shaped to strip or strand shape, only is suitable for powdery or paste and uses.The special public clear 44-11009 (Ag=47-70 of Japan Patent for another example, Cu=25-40, Sn=2-6, In=3-7), the spy opens clear 51-132147 (Ag=28.8-50.4, Cu=11.2-19.6, Sn=15-30, In=15-30), the spy opens clear 63-53915 (Ag=7.5-35, Cu=40-60, Sn=25-37.5) and JP05132369 (Ag=18-60, Cu=20-50, Sn=18-35 Ge=1-5) is the Cu-Ag-Sn base solder that can be used for the electrovacuum field, but they or contain a large amount of Ag, or cause material too crisp because of containing a large amount of elements such as Sn, and can not be shaped to strip or strand shape, thus limited their application widely.
It is low to the objective of the invention is to seek a kind of silver content, has low melting point, low-vapor pressure, and can be shaped to strip or strand shape, and can be used for the electrovacuum field again, can replace the Cu base solder of AgCu28.
Solder of the present invention, its composition range are Ag:5-25wt%, Sn:10-25wt%, and In:5-10wt%, surplus is Cu.The adding of In can reduce molten point of the present invention in the middle of this, makes molten point＜800 of the present invention ℃, in addition, also can improve plasticity of the present invention and wetability.B that on this basis can be by adding 0.003-0.5wt% or the Fe of Ce and 0.003-1.0wt%, Ni, a kind of among the Co or several further improve its wetability, performances such as joint filling.
The preparation of solder mainly comprises two aspects: 1). the melting of solder.With the raw material fine copper, fine silver, pure tins etc. clean up and dry with acid, and batching on request earlier places copper then in the alumina crucible of sky induction furnace and is heated to whole fusings, adds deoxidier, adds clout again, stirs composition and is cast into ingot after evenly; 2). the moulding of solder.The ingot casting that above-mentioned melting casting is formed, cut into certain shape on request, produce the technology of amorphous or crystallite strip again with rapid solidification, solder is made thick 0.05-0.15mm, composition is even, strip with better toughness plasticity, toughness plasticity is meant when strip can be bent to radius of curvature is 20 times of thickness and does not rupture preferably.Solder also can adopt conventional method to be processed into firelight or sunlight shape or strip use in addition.Certainly it can replace the AgCu28 solder too and be used for other field.
The copper base solder that the present invention developed is compared with existing solder, has following characteristics:
1). low silver content and the low indium amount that contains make the invention cost be significantly less than existing vacuum seal solder.
2). its fusion temperature, to oxygen-free copper, can cut down, the wetability of nickel and joint filling are suitable with the AgCu28 solder.
3). can be in atmosphere (use scaling powder) and inert atmosphere, contain H
2Atmosphere, soldering in the vacuum.
4). replace the sealing-in that AgCu28 is used for ceramic cartridge with this solder, every performance (as weld appearance, air-tightness, sealing strength, circulation of heatproof degree and vibration performance) all meets the requirements of the standard.
Embodiment:
Getting a solder of the present invention, is 20wt%Sn by its composition, 10wt%Ag, and 5wt%In, 0.005wt%B, surplus Cu batching is smelted into alloy-steel casting with said method.At first measured some basic properties of solder itself, comprised fusion temperature, to nickel, the wetability that can cut down and joint filling compare with AgCu28 simultaneously.Fusion temperature is to adopt differential thermal analysis to measure in the base.Wetability and joint filling are to measure according to the requirement of GB11364-89, and wetability characterizes with the spreading area S of solder on mother metal, and joint filling characterizes with the joint filling length L, the used solder of wettability test is 0.1g, it is 0.8g that used solder is tested in joint filling, and test temperature is 840 ℃, heats in the nitrogen atmosphere.Table 1 is its experimental result
The basic property of table 1 solder
| Liquidus temperature | Spreading area S (cm 2) | Joint filling length L (cm) | |
| Mother metal Ni mother metal Kovar | Mother metal Ni mother metal Kovar | ||
| New solder AgCu28 | 766℃ 779℃ | 3.92 3.53 5.81 1.54 | 7.8 8.7 8.0 7.7 |
It can be seen from the table, new solder has the liquidus temperature close with AgCu28, the wetability of Ni is slightly poorer than AgCu28, but the Kovar wetability is better than AgCu28, and gap filling performance and AgCu28 are suitable.
With the preparation of above-mentioned solder and be processed into thick 0.12mm, in, external diameter can be not Wei Φ 30, the ring plate of Φ 40, try out in the sealing-in of power semiconductor device with ceramic cartridge, and according to the requirement of professional standard ZBK46003-87 to shell, to its weld appearance, weld strength, temperature cycling tests etc. detect, below be concrete testing result: with new solder at 840 ℃, 10 of soldering shells in the cracked ammonium atmosphere, weld appearance all satisfies the requirement of standard, be that weld seam between metal and pottery is bright and clean, smoothly, do not have and gather residue, solder does not have splatter, and weld seam does not have through hole, the stream ball, the slit, and do not have blind hole.10 shells are hunted leak with the helium mass analyzer tracer gas technique, and the result shows that the shell leak rate all is lower than 1 * 10
-7Pa.m
2/ S, through temperature cycles, after the vibration test, outward appearance and air-tightness still meet the requirements.Measured weld strength at last, weld strength is weighed with ceramic standard tensile members intensity.
Result of the test such as table 2, five tensile members as can be seen, its intensity is all greater than desired 400kg/cm
2
Above result solder of the present invention can replace the AgCu28 solder and be used for the sealing-in of power semiconductor device with ceramic cartridge.Certainly it can be applicable to other brazed copper too, oxygen-free copper, and nickel can cut down, the occasion of metallized ceramic.
The intensity of the ceramic standard tensile members of table 2
| Test piece number (Test pc No.) | 1 | 2 | 3 | 4 | 5 |
| Tensile strength (kg/cm 2) fracture place | 503.9 metal layer | 1088.8 ceramic basic unit | 787.4 metal layer | 809.8 metal layer | 575.9 metal layer |
Claims (3)
1. copper base solder that is used for vacuum, this solder includes silver, tin, indium is characterized in that compositional range is Ag:5-25wt%, Sn:10-25wt%, the In:5-10wt% surplus is Cu.
2. a kind of copper base solder that is used for vacuum according to claim 1 is characterized in that can adding in the above-mentioned solder B or the Ce of 0.003-0.5wt%.
3. solder according to claim 1 and 2 is characterized in that the solder after the moulding is strip or strand shape.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111020A CN1037825C (en) | 1995-04-26 | 1995-04-26 | Copper-base solder-silver substituted solder for electrical vacuum with low melting point, low vapour pressure and ductility |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111020A CN1037825C (en) | 1995-04-26 | 1995-04-26 | Copper-base solder-silver substituted solder for electrical vacuum with low melting point, low vapour pressure and ductility |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1120480A CN1120480A (en) | 1996-04-17 |
| CN1037825C true CN1037825C (en) | 1998-03-25 |
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ID=5078342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95111020A Expired - Fee Related CN1037825C (en) | 1995-04-26 | 1995-04-26 | Copper-base solder-silver substituted solder for electrical vacuum with low melting point, low vapour pressure and ductility |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1037825C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100464001C (en) * | 2006-04-11 | 2009-02-25 | 中国科学院金属研究所 | High-strength high-conductivity oxidation-resisting low-silver copper-base alloy and preparation thereof |
| CN101569967B (en) * | 2009-06-16 | 2011-05-11 | 贵研铂业股份有限公司 | Copper-silver alloy low vapor pressure brazing filler metal containing Si and Ga and its uses |
| CN102029484B (en) * | 2010-12-15 | 2012-11-07 | 常熟市双华电子有限公司 | Low-silver electro vacuum brazing filler metal used for sealing weld of electronic device |
| CN103909363A (en) * | 2014-04-01 | 2014-07-09 | 金华市三环焊接材料有限公司 | Cadmium-free low-silver solder containing tin, manganese and indium |
| KR101671062B1 (en) * | 2014-08-18 | 2016-10-31 | 주식회사 경동원 | Lead-free solder composition and manufacturing method of lead-free solder composition |
| CN108340094B (en) * | 2017-01-23 | 2020-11-17 | 北京有色金属与稀土应用研究所 | Ag-Cu-In-Sn-Ti alloy solder and preparation method and application thereof |
| CN110952017B (en) * | 2019-12-27 | 2020-10-09 | 华北水利水电大学 | High-entropy ultra-silver solder alloy and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU637217A1 (en) * | 1977-04-18 | 1978-12-15 | Педприятие П/Я В-8584 | Solder for soldering components of electric discharge devices |
-
1995
- 1995-04-26 CN CN95111020A patent/CN1037825C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU637217A1 (en) * | 1977-04-18 | 1978-12-15 | Педприятие П/Я В-8584 | Solder for soldering components of electric discharge devices |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1120480A (en) | 1996-04-17 |
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