CN1027626C

CN1027626C - Weldable ceramic Sn base active medium solder

Info

Publication number: CN1027626C
Application number: CN 92106127
Authority: CN
Inventors: 冼爱平; 斯重遥
Original assignee: Institute of Metal Research of CAS
Current assignee: Institute of Metal Research of CAS
Priority date: 1992-04-11
Filing date: 1992-04-11
Publication date: 1995-02-15
Anticipated expiration: 2007-04-11
Also published as: CN1077151A

Abstract

The present invention belongs to the technical field of soldering, namely provides a Sn-base active solder which is suitable for the direct soldering of ceramic material and metal material. The solder alloy provided by the present invention has the following formulation with the atomic percent of active elements: the third components: Sn of 0.5: 100: 40%, wherein the active elements are Ti, Zr, Hf or the composition of Ti, Zr and Hf; the third components are Ag, Cu, Ni, In or the composition of Ag, Cu, Ni and In. The present invention can be used for the direct soldering of oxide ceramics and non-oxide ceramics with metal, obtained joints have the advantages of firm connection and low residual stress.

Description

Weldable ceramic Sn base active medium solder

The invention belongs to welding technology field, specifically just provided a kind of Sn based active solder, be applicable to the direct soldering of various ceramic materials and metal.

Solder is a kind of practical technique of having many uses, be very suitable for making butt joint intensity and the not too high middle or small metal parts of serviceability temperature requirement, the particularly connection of plain conductor, common soft solder, as Sn-Pb, a major defect of alloys such as Sn-Bl is them not to adhere in that metal oxide surface is all both nonwetting yet.And common metal surface oxidation rate in air is exceedingly fast; so reality usually needs to adopt suitable brazing flux when using these solder brazings; as add inorganic salts or inorganic acid (comprising zinc chloride, ammonium chloride, stannous chloride, sodium chloride and potassium chloride, potassium chloride, fluoboric acid etc.); and organic brazing flux such as rosin etc. remove one deck thin oxide film of metal surface and are protected unsalted surface, just can make solder take place well wetting in the metal surface and adhere to.These brazing fluxes not only corrode work, contaminated environment, and have increased the difficulty of after welding treatment.Especially, because common soft solder is not wetting on pottery, be impossible so adopt these solder brazing ceramic materials, a kind of indirect soldering tech, promptly ceramic surface adopts physics or chemical method preplating layer of metal rete, for example EP0160301A ₂The technology that is provided can realize metal and ceramic soldering, and the shortcoming of this technology path is conspicuous, and is promptly not only technical very complicated, and production cost also improves rapidly.A kind of metal and the ceramic directly technology of soldering promptly adopt as GB2066291A, EP1044623A ₂And EP0135603A ₁The active metallic soldering material that is provided, because these solders are can be on ceramic surface wetting and adhere to, so they can directly carry out soldering to not metallized pottery, advantage technically is conspicuous, but a major defect of these technology is because these solders have high melt point and intensity, so residual stress is very high in the metal/ceramic joint that it welded, under this high residual stress effect, near the joint ceramic material damage is serious, institute's plumb joint is usually disrumpent feelings at a ceramic side low stress, in some occasion, even in the cooling of joint postwelding, it is disrumpent feelings voluntarily promptly to produce cracking near the pottery the joint.For fear of high residual stress, GB2151173A proposes to adopt the soft interlayer of one deck to come loose possible residual stress.Yet because the insertion in intermediate layer makes joint design complicated, connecting boundary's number increases, and produces a series of additional Welding Metallurgy problems therefrom.It is the active solder of base with the Ag-Sn alloy that the spy opens clear 64-71592 proposition a kind of, and wherein active element is Si, Mg, Ti, Zr, Nb, Ce, Ca, Ba, Li and La, this solder can be realized metal and ceramic direct soldering, and the joint residual stress is lower, but owing to contain Ag amount more (20～60%) in the solder, solder goes the assisted malleability on the pottery relatively low, and welding requirements is at certain pressure (0.1Kgf/mm ²) under carry out, make welding procedure complicated, and the solder cost is also higher relatively, Te Kaiping 1-95893 proposes a kind of Sn-NI-Ti active medium solder (0.1～5%Ti, 0.02～12%Ni, surplus is Sn), DE3641679Al proposes two kinds of Sn based active solder (86～95%Sn, 1～13%Ag, 1～10%Ti and 86～95%Sn, 1～12%Ag, 1～5%Cu, 1～10%Ti), wetting and adhesion all can directly take place in these solders on pottery, can be used for the direct welding of pottery and metal simultaneously, and residual stress is lower, yet it is relatively low at the ceramic surface bonding strength as the Sn base solder of reactive metal to add Ti separately, and joint is often peeled off from the metal and the interface of pottery.

The object of the present invention is to provide a kind of soft active metallic soldering material, make and refuse under the metallized situation of elder generation at no brazing flux and ceramic surface, these solders are can be directly wetting and adhere on pottery, and keep joint that lower welding residual stress is arranged, be fit to various purpose metals and ceramic welding joint to make easily.

The invention provides a kind of Sn base binary or ternary active solder, be specially adapted to metal and the direct welding of making pottery and building, it is characterized in that the solder prescription is as follows: (atomic percent)

Hf Ni Sn

0.5～8% 0～8% surplus

The optimum range of Hf is 2～5%.Solder provided by the invention can adopt the tungsten arc melting under suitable method such as vacuum melting or the argon shield to be prepared, and when this solder is used for the soldering of pottery, needs to carry out under vacuum or inert gas shielding condition, and temperature range is: 1000K～1300K.This solder has good wettability at multiple ceramic surface, to without the ceramic surface of metalized in advance, the angle of wetting of solder can be lower than below 20 degree, solder has good bonding strength on pottery simultaneously, measure with little joint (3 * 4 * 40) four-point bending method, generally can reach 40MPa, reach as high as 150MPa in some cases.Solder provided by the invention has wider adaptability to ceramic material, comprise oxide ceramics, for example aluminium oxide, corundum, magnesia, mullite, zirconia, quartz etc., and non-oxide ceramics such as diamond, graphite, silicon nitride, Sialon and carborundum etc. describe embodiment below in detail.

Embodiment

Preparing a kind of composition is 4%Hf, 0.36Ni, and all the other are the alloy of Sn, and are under the Ar gas shiled, even with the tungsten arc melting.Get a fritter solder and place brown corundum ceramic (Al ₂O ₃+ 2wt%Cr ₂O ₃) on, under vacuum, be heated to 1200K insulation 20min after, solder is good in the ceramic surface wetability, and realizes firm adhesion.

Claims

1, a kind of Sn base binary or ternary active solder are specially adapted to metal and the direct welding of making pottery and building, and it is characterized in that the solder prescription is as follows: (atomic percent)

Hf Ni Sn

0.5～8% 0～8% surplus

2, according to the described active solder of claim 1, it is characterized in that: the optimum range of Hf is 2～5%.