CN102699567A - Zirconium-containing copper silver titanium solder alloy - Google Patents
Zirconium-containing copper silver titanium solder alloy Download PDFInfo
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- CN102699567A CN102699567A CN2012101958502A CN201210195850A CN102699567A CN 102699567 A CN102699567 A CN 102699567A CN 2012101958502 A CN2012101958502 A CN 2012101958502A CN 201210195850 A CN201210195850 A CN 201210195850A CN 102699567 A CN102699567 A CN 102699567A
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Abstract
The invention discloses a zirconium-containing copper silver titanium solder alloy. The zirconium-containing copper silver titanium solder alloy comprises the following components by mass percent: 10-45% of Ag, 1-4% of Ti, 0.5-5% of Zr and Cu for the rest. A vacuum melting and argon shield casting mode is adopted, silver and copper are molten at first and then titanium and zirconium are added. The zirconium-containing copper silver titanium solder alloy can be used for directly soldering copper alloys, iron steel, ceramics and diamonds. The zirconium-containing copper silver titanium solder alloy has the advantages as follows: the cost is low; a connector is high in mechanical strength, has smooth surface, is stable in quality and is good in uniformity after the copper alloys are soldered by the zirconium-containing copper silver titanium solder alloy; and the joint clearances can be fully filled up. The zirconium-containing copper silver titanium solder alloy can replace the conventional copper silver titanium solder and is suitable for large-scale industrial application.
Description
Technical field
The present invention relates to a kind of copper silver is alloy, is meant a kind of copper silver titanium solder alloy that contains zirconium especially, belongs to intermediate temperature solder material technology field.
Background technology
Characteristics such as ceramic material has wear-resisting, and is corrosion-resistant, high temperature resistant, good insulating and being widely used in modern industry and the sciemtifec and technical sphere have shown wide application prospect.But higher because of ceramic material hardness, bad plasticity is difficult to distortion and cut.Therefore, quite a lot on practical applications is to adopt pottery and metal or pottery and the ceramic composite component of forming, and for this reason, must solve pottery and metal and the ceramic problem that is connected with ceramic phase.Former studies shows, the welding of pottery and metal or pottery and pottery, and what tool potentiality, employing were more is active brazing filler metal.At present, in directly soldering connected, the Ag-Cu-Ti solder was that ceramic soldering is generally acknowledged best active solder.Ag-Cu-Ti alloy activated solder has less infiltration angle, and is best to the wellability of pottery.It broken away between the pottery and pottery and metal between must carry out the complex techniques process of metalized during welding earlier at ceramic surface, can realize that pottery and pottery, pottery are successful with a soldering of metal assembly.
Silver content surpasses 60% in the existing copper silver titanium solder alloy, like Ag71Cu27.5Ti1.5, Ag70Cu28Ti2, AgCuTi34.5-1.5, and AgCuTi26.5-3 and Ag-CuTil0-4 alloy etc., the alloy of these high silver contents has improved the production cost of material.In addition, research shows, is to add Ti in the alloy at Ag-Cu, has formed Cu
3Compound phase between the Ti reguline metal, this compound is enriched in brazing process on the interface of matrix and solder, has reduced the intensity of soldering head.Therefore how on the basis of the intermediate temperature solder performance that guarantees alloy, reduce the content of silver in the alloy, the intensity that improves the soldering head becomes one of important research contents.Existing document shows, both at home and abroad also not through in the silver-bearing copper titanium alloy, adding zirconium, with the content of reduction Ag and the side effect of Ti, improves the report of the combination property of alloy at present.
Summary of the invention
The object of the invention provides a kind of copper silver titanium solder alloy that contains zirconium to prior art deficiency and defective; Brazing filler metal alloy provided by the invention through the alloying of zirconium, reduces the side effect of silver content and titanium, improves the brazing property of brazing filler metal alloy, reduces copper silver titanium solder alloy manufacturing cost, satisfies industrial needs.
A kind of copper silver titanium solder alloy that contains zirconium of the present invention comprises following component, forms by mass percentage:
Ag:10~45%,
Ti：1~4%，
Zr:0.5 ~ 5%, surplus are Cu.
A kind of copper silver titanium solder alloy that contains zirconium of the present invention comprises following component, forms by mass percentage:
Ag:15~40%,
Ti：1.5~3.5%，
Zr:0.8 ~ 4.5%, surplus are Cu.
A kind of copper silver titanium solder alloy that contains zirconium of the present invention comprises following component, forms by mass percentage:
Ag:20~30%,
Ti：2~3%，
Zr:1.5 ~ 3%, surplus are Cu.
A kind of preparation method who contains the copper silver titanium solder alloy of zirconium of the present invention is: the alloy compositions proportioning by design is got each component Ag, Ti, Zr, Cu; Vacuum melting argon shield casting down obtains ingot casting; Wherein, Ti adds with the titanium sponge form, and Ag adds with the form of cathode copper with fine silver, Cu, and Zr adds with the form of Cu-Zr intermediate alloy.
Alloy component of the present invention and percentage by weight are: 45%Ag, and 4%Ti, 1%Zr, when all the other are Cu, 763 ℃ of the fusing points of the brazing filler metal alloy that casting obtains.Through with the brass alloys soldering after, the shear strength of solder joint is 96MPa, the wettability of solder and matrix alloy is good, does not find Cu
3Ti is enriched on the interface mutually.
Alloy component of the present invention and percentage by weight are: 27.5%Ag, and 2%Ti, 2%Zr, when all the other are Cu, 774 ℃ of the fusing points of the brazing filler metal alloy that casting obtains.Through with the brass alloys soldering after, the shear strength of solder joint is 113MPa, the wettability of solder and matrix alloy is good, does not find Cu
3Ti is enriched on the interface mutually.
Alloy component of the present invention and percentage by weight are: 15%Ag, and 1.5%Ti, 4%Zr, when all the other are Cu, 786 ℃ of the fusing points of the brazing filler metal alloy that casting obtains.Through with the brass alloys soldering after, the shear strength of solder joint is 98MPa, the wettability of solder and matrix alloy is good, does not find Cu
3Ti is enriched on the interface mutually.
Compared with prior art, the invention has the advantages that:
The present invention adds zirconium, through the alloying of zirconium owing to adopt the said components proportioning on the basis of existing copper silver titanium alloy; Can effectively reduce the side effect of silver content and titanium; Significantly improve the brazing property of brazing filler metal alloy, and reduce copper silver titanium solder alloy manufacturing cost, the alloying mechanism of zirconium is sketched in following among the present invention: because Ti and Zr are subordinate to same subgroup in the periodic table of elements; Has similar character; The adding of Zr destroyed the rock-steady structure of Cu3Ti, the contention electronics, upset Ti, Ag, Cu between the balance of Cheng Jian; Because the bond energy of Cu-Zr is bigger than the bond energy of Cu-Ti and Zr-Ti, then the Cu atom around the Ti will trend towards around the Zr, thereby the Cu atomicity around the Ti is reduced; The adding of Zr will make Ti activity increase, and block Cu3Ti phase amount reduces, and size is little; Ag, Cu, Ti, four kinds of atoms of Zr form (Cu, Ag) 5 (Ti that new small and dispersed distributes through being reassembled into key; Zr) phase; New looks exists as the dispersion-strengtherning phase with a kind of form of heterogeneous particles at first, has increased nucleation rate, and then has reduced the size of crystal grain; The cenotype that small and dispersed distributes helps forming the Ke Chuier air mass and produces pinning effect, strengthens dispersion-strengthened action, effectively stops dislocation motion and crystal boundary slippage, and dislocation mobile drag is under external force increased, thereby has improved the mechanical property of brazing filler metal alloy; The interpolation of Zr simultaneously; The activity of raising solder that can be direct and indirect, the homogenising degree of the elemental diffusion degree of depth and tissue is high, helps quickening the diffusion and the interfacial reaction of atom in the high temperature brazing process; This just makes, and conversion zone is interactional to double; React more thorough, help forming the conversion zone of continuous densification, thereby reduce the residual stress in the joint and improve strength of joint.For these reasons, on the basis of copper silver titanium alloy, add zirconium, reduce the content of silver, utilize the active function of zirconium, reduce block precipitated phase Cu in the alloy
3The content of Ti, form that new small and dispersed distributes (Cu, Ag)
5(intensity of raising brazing filler metal alloy improves brazing property for Zr, Ti) phase, and existing industrial equipment capable of using carries out large-scale production.
Description of drawings
Accompanying drawing 1: for the alloy casting state of Comparative Examples preparation of the present invention is organized photo;
Accompanying drawing 2: for the alloy casting state of the embodiment of the invention 2 preparations is organized photo;
Accompanying drawing 3: for the alloy casting state of the embodiment of the invention 3 preparations is organized photo;
Accompanying drawing 4: for the alloy casting state of the embodiment of the invention 4 preparations is organized photo;
Can find out in the accompanying drawing 1, contain block Cu in the as-cast structure of the alloy of Comparative Examples preparation
3The Ti phase;
In the accompanying drawing 2,3,4, can find out that the alloy casting state of embodiment 2,3,4 preparations is organized and do not contained block Cu
3The Ti phase;
In Fig. 4, can see contain in the alloy casting state tissue of embodiment 4 preparation the small and dispersed distribution (Cu, Ag)
5(Zr, Ti) phase.
The specific embodiment
In conjunction with method of the present invention following instance is provided:
Embodiments of the invention are at copper silver titanium alloy (Ag:10 ~ 45%; Ti:1 ~ 4%; Surplus is Cu) add the zirconium of different content in the batching, its composition is different from casting copper silver titanium alloys such as existing Ag71Cu27.5Ti1.5, embodiment 1,2,3,4,5 and Comparative Examples alloying ingredient such as table 1.Embodiment and the preparation of Comparative Examples alloy are all adopted and are cast into round base under the vacuum melting argon shield.The vacuum melting temperature is 1200 ~ 1500 ℃, and vacuum is 0.001 ~ 0.1 handkerchief; Specify as follows:
Comparative Examples
Alloying ingredient (raw material is: fine silver, cathode copper, titanium sponge) melting in vacuum induction melting furnace, argon shield is cast into ingot casting.789 ℃ of the fusing points of brazing filler metal alloy, Vickers hardness are 161HV.Brazing filler metal alloy applies to the connection of brass alloy material, and shear strength test shows, the shear strength of solder joint are 70MPa, solder and welding material wetting good, but a large amount of block Cu are arranged on solder and the welding material interface
3The enrichment of Ti phase.
Embodiment 1
The batching of alloy (raw material is: fine silver, cathode copper, titanium sponge, Cu-50Zr intermediate alloy) melting in vacuum induction melting furnace, argon shield is cast into ingot casting.781 ℃ of the fusing points of brazing filler metal alloy, Vickers hardness are 178HV.Brazing filler metal alloy applies to the connection of brass alloy material, and shear strength test shows, the shear strength of solder joint are 81MPa, solder and welding material wetting good, and do not have Cu on solder and the welding material interface
3The enrichment of Ti phase.
Embodiment 2
The batching of alloy (raw material is: fine silver, cathode copper, titanium sponge Cu-50Zr intermediate alloy) melting in vacuum induction melting furnace, argon shield is cast into ingot casting, alloy casting state knot of tissue member accompanying drawing 2.786 ℃ of the fusing points of brazing filler metal alloy, Vickers hardness are 198HV.Brazing filler metal alloy applies to the connection of brass alloy material, and shear strength test shows, the shear strength of solder joint are 96MPa, solder and welding material wetting good, and do not have Cu on solder and the welding material interface
3The enrichment of Ti phase.
Embodiment 3
The batching of alloy (raw material is: fine silver, cathode copper, titanium sponge Cu-50Zr intermediate alloy) melting in vacuum induction melting furnace, argon shield is cast into ingot casting, alloy casting state knot of tissue member accompanying drawing 3.774 ℃ of the fusing points of brazing filler metal alloy, Vickers hardness are 211HV.Brazing filler metal alloy applies to the connection of brass alloy material, and shear strength test shows, the shear strength of solder joint are 113MPa, solder and welding material wetting good, and do not have Cu on solder and the welding material interface
3The enrichment of Ti phase.
Embodiment 4
The batching of alloy (raw material is: fine silver, cathode copper, titanium sponge Cu-50Zr intermediate alloy) melting in vacuum induction melting furnace, argon shield is cast into ingot casting, alloy casting state knot of tissue member accompanying drawing 4.763 ℃ of the fusing points of brazing filler metal alloy, Vickers hardness are 197HV.Brazing filler metal alloy applies to the connection of brass alloy material, and shear strength test shows, the shear strength of solder joint are 98MPa, solder and welding material wetting good, and do not have Cu on solder and the welding material interface
3The enrichment of Ti phase.
Embodiment 5
The batching of alloy (raw material is: fine silver, cathode copper, titanium sponge Cu-50Zr intermediate alloy) melting in vacuum induction melting furnace, argon shield is cast into ingot casting.758 ℃ of the fusing points of brazing filler metal alloy, Vickers hardness are 199HV.Brazing filler metal alloy applies to the connection of brass alloy material, and shear strength test shows, the shear strength of solder joint are 94MPa, solder and welding material wetting good, and do not have Cu on solder and the welding material interface
3The enrichment of Ti phase.
Table 1 (mass percent)
| Alloy | Ag | Ti | Zr | Cu |
| The comparative example | 70 | 4 | 0 | Surplus |
| Embodiment 1 | 45 | 4 | 0.5 | Surplus |
| Embodiment 2 | 45 | 4 | 1 | Surplus |
| Embodiment 3 | 27.5 | 2 | 2 | Surplus |
| Embodiment 4 | 15 | 1.5 | 4 | Surplus |
| Embodiment 5 | 10 | 1 | 5 | Surplus |
Claims (6)
1. a copper silver titanium solder alloy that contains zirconium comprises following component, forms by mass percentage:
Ag:10~45%,
Ti：1~4%，
Zr:0.5 ~ 5%, surplus are Cu.
2. a kind of copper silver titanium solder alloy that contains zirconium according to claim 1 comprises following component, forms by mass percentage:
Ag:15~40%,
Ti：1.5~3.5%，
Zr:0.8 ~ 4.5%, surplus are Cu.
3. a kind of copper silver titanium solder alloy that contains zirconium according to claim 1 comprises following component, forms by mass percentage:
Ag:20~30%,
Ti：2~3%，
Zr:1.5 ~ 3%, surplus are Cu.
4. a kind of copper silver titanium solder alloy that contains zirconium according to claim 1 comprises following component, forms by mass percentage:
45%Ag, 4%Ti, 1%Zr, all the other are Cu; The fusing point of alloy is 763 ℃; After the brass alloys soldering, the shear strength of solder joint is 96MPa.
5. a kind of copper silver titanium solder alloy that contains zirconium according to claim 1 comprises following component, forms by mass percentage:
27.5%Ag, 2%Ti, 2%Zr, all the other are Cu; The fusing point of alloy is 774 ℃; After the brass alloys soldering, the shear strength of solder joint is 113MPa.
6. a kind of copper silver titanium solder alloy that contains zirconium according to claim 1 comprises following component, forms by mass percentage: 15%Ag, and 1.5%Ti, 4%Zr, all the other are Cu; The fusing point of alloy is 786 ℃; After the brass alloys soldering, the shear strength of solder joint is 98MPa.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084591A (en) * | 2014-07-03 | 2014-10-08 | 哈尔滨工业大学 | Method for preparing Ag-Cu-Ti nano-alloy solder |
| CN105834613A (en) * | 2016-05-20 | 2016-08-10 | 南京理工大学 | Solder special for high-frequency soldering of four-way valve |
| CN106041238A (en) * | 2016-06-13 | 2016-10-26 | 西安理工大学 | Probe shell structure for measuring specific retention of petroleum well and seal welding material of probe shell structure |
| US11702723B2 (en) | 2019-01-24 | 2023-07-18 | Subodh Subas Pethe | Silver alloy with improved mechanical properties |
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| CN1396037A (en) * | 2002-08-09 | 2003-02-12 | 中国科学院上海硅酸盐研究所 | High-temp soldering method for aluminium nitride and copper |
| CN102319964A (en) * | 2011-08-06 | 2012-01-18 | 郑州机械研究所 | Active core silver solder for soldering ceramics and preparation method thereof |
| CN102448663A (en) * | 2009-05-27 | 2012-05-09 | 京瓷株式会社 | Solder material, heat dissipation base using same, and electronic device |
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2012
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH09132473A (en) * | 1995-11-07 | 1997-05-20 | Shichizun Iwate:Kk | Brazing filler metal for ceramics |
| JPH10193211A (en) * | 1997-01-09 | 1998-07-28 | Mitsubishi Materials Corp | Cemented carbide-made cutting tool having excellent brazing connection strength in cutting edge piece |
| CN1094810C (en) * | 1999-12-27 | 2002-11-27 | 华南理工大学 | Active solder and its preparation |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084591A (en) * | 2014-07-03 | 2014-10-08 | 哈尔滨工业大学 | Method for preparing Ag-Cu-Ti nano-alloy solder |
| CN104084591B (en) * | 2014-07-03 | 2016-08-17 | 哈尔滨工业大学 | A kind of method preparing Ag-Cu-Ti Nanoalloy solder |
| CN105834613A (en) * | 2016-05-20 | 2016-08-10 | 南京理工大学 | Solder special for high-frequency soldering of four-way valve |
| CN105834613B (en) * | 2016-05-20 | 2018-10-02 | 南京理工大学 | A kind of solder being exclusively used in four-way valve high frequency brazing |
| CN106041238A (en) * | 2016-06-13 | 2016-10-26 | 西安理工大学 | Probe shell structure for measuring specific retention of petroleum well and seal welding material of probe shell structure |
| CN106041238B (en) * | 2016-06-13 | 2018-09-25 | 西安理工大学 | A kind of oil well surveys specific retention probing shell structure and its sealing materials |
| US11702723B2 (en) | 2019-01-24 | 2023-07-18 | Subodh Subas Pethe | Silver alloy with improved mechanical properties |
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Application publication date: 20121003 |