CN103341700A - Co-Ti-Nb-based high-temperature brazing filler metal - Google Patents
Co-Ti-Nb-based high-temperature brazing filler metal Download PDFInfo
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- CN103341700A CN103341700A CN2013103251596A CN201310325159A CN103341700A CN 103341700 A CN103341700 A CN 103341700A CN 2013103251596 A CN2013103251596 A CN 2013103251596A CN 201310325159 A CN201310325159 A CN 201310325159A CN 103341700 A CN103341700 A CN 103341700A
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Abstract
The invention relates to a brazing material and in particular relates to Co-Ti-Nb-based high-temperature brazing filler metal. Aiming at solving the problem that the strength of a high-temperature structural ceramic joint brazed by using conventional brazing filler metal is low in a high-temperature environment, the invention provides the Co-Ti-Nb-based high-temperature brazing filler metal. The Co-Ti-Nb-based high-temperature brazing filler metal provided by the invention is produced from the following components in parts by weight: 8.5-45 parts of Nb, 33-50 parts of Co and 22-41.5 parts of Ti. According to the Co-Ti-Nb-based high-temperature brazing filler metal, based on Co-50 Ti (at %), an element Nb which can be infinitely solid melted with an active element Ti is added. By adding the active element Nb, on the one hand, the activity of the element Ti is improved, and on the other hand, the melting point of the brazing filler metal is reduced, and the strength of the high-temperature structural ceramic joint brazed by using the brazing filler metal in the high-temperature environment is enhanced. The Co-Ti-Nb-based high-temperature brazing filler metal is applied to the field of brazing.
Description
Technical field
The present invention relates to a kind of brazing material.
Background technology
Structural ceramics is as a kind of new structural material, unique excellent properties such as, high strength high temperature resistant with it, exceptional hardness, wear-resistant, anticorrosive and low thermal conductance, in industries such as national defence, the energy, Aero-Space, machinery, petrochemical industry, metallurgy, electronics, demonstrate wide application prospect day by day, cause the attention of each industrially developed country, competitively drop into great amount of manpower and material resources studied.
Because the poor processability of ceramic material, the part that the low heat-resistant impact ability of ductility and toughness is weak and manufacturing dimension is big and complex-shaped is shortcoming such as difficulty comparatively, need form that composite construction is used with metal material usually or the manufacturing that is connected to realize complex component by pottery self.Therefore the connectivity problem that solves pottery/pottery, ceramic/metal is to push use high-temperature structural ceramics one of to key technology that must solve.
Soldering and diffusion welding (DW) are existing main methods of attachment about pottery/pottery and ceramic/metal, and present result of study shows, the intensity of pottery/pottery, ceramic/metal jointing and heat resisting temperature are compared with practical requirement and still had big gap.In the soldering research field, be to use traditional Ag-Cu-Ti, Cu-Ti active solder etc. more in the connection of pottery.Though some the soldered fitting intensity that obtains is higher, the high-temperature behavior of joint is poor, and serviceability temperature is low, thereby has restricted the performance of structural ceramics high-temperature behavior.So the research and development of high-temp solder become a kind of inevitable trend.
At present, both at home and abroad the research of high-temp solder is progressively carried out, more common have Ni-Cr-Si system, Au-Ni-V system, Pd-Co, Ni-Ti and a Co-Ti isoreactivity solder.The Au-Ni-V solder is connecting Si
3N
4And Si
3N
4The time, room temperature four-point bending intensity is 393MPa, and 700 ℃ the time intensity less than 40% of room temperature; The Ni-Cr-Si solder is connecting Si
3N
4And Si
3N
4The time, 700 ℃ of high temperature four-point bending intensity are 200MPa, and room temperature is less than 120MPa, and strength of parent is lower relatively; When solder is Pd-Co, the connection mother metal is ZrB
2During-SiC pottery, its joint room temperature shearing strength is 80MPa.Cause that the lower main cause of intensity is the brazing temperature height under the high-temperature structural ceramics joint room temperature of these solder brazings or the hot environment, joint generates frangible compounds easily, and in Ni-Ti and the Co-Ti brazing filler metal active element Ti easily with Ni or Co formation stable compound, thereby reduced the activity of Ti.
Summary of the invention
The present invention will solve the lower problem of intensity under the high-temperature structural ceramics joint hot environment of traditional solder brazing, and it is high-temp solder that a kind of Co-Ti-Nb is provided.
A kind of Co-Ti-Nb of the present invention is high-temp solder according to mass fraction is to be made by the titanium of 8.5～45 parts of niobiums, 33～50 parts of cobalts and 22～41.5 parts.
The present invention is based on Co-50Ti(at%), add the infinitely solid molten Nb element of energy and active element Ti.The adding of active element Nb has improved on the one hand the activity of Ti element, has then reduced the fusing point of solder on the other hand, has improved intensity under the high-temperature structural ceramics joint hot environment of solder brazing.
Description of drawings
Fig. 1 is the microphoto of organizing of high-temp solder for the Co-Ti-Nb of test 1 preparation;
Fig. 2 is the microphoto of organizing of high-temp solder for the Co-Ti-Nb of test 2 preparations;
Fig. 3 is the microphoto of organizing of high-temp solder for the Co-Ti-Nb of test 3 preparations;
Fig. 4 is the microphoto of organizing of high-temp solder for the Co-Ti-Nb of test 4 preparations;
Fig. 5 is the TG-DTA resolution chart of high-temp solder for the Co-Ti-Nb of test 1～test 4 preparations, wherein a is the TG-DTA test curve of high-temp solder for the Co-Ti-Nb of test 1 preparation, b is the TG-DTA test curve of high-temp solder for the Co-Ti-Nb of test 2 preparations, c is the TG-DTA test curve of high-temp solder for the Co-Ti-Nb of test 3 preparations, and d is the TG-DTA test curve of high-temp solder for the Co-Ti-Nb of test 4 preparations;
Fig. 6 is high-temp solder soldering C for the Co-Ti-Nb that adopts test 1 preparation
fThe micro-organization chart of the joint that/SiC composite and metal Nb obtain; Wherein a is C
f/ SiC composite, b are the intermediate layer, and c is metal Nb.
The specific embodiment
The specific embodiment one: a kind of Co-Ti-Nb of present embodiment is high-temp solder according to mass fraction is to be made by the titanium of 8.5～45 parts of niobiums, 33～50 parts of cobalts and 22～41.5 parts.
Present embodiment is based on Co-50Ti(at%), add the infinitely solid molten Nb element of energy and active element Ti.The adding of active element Nb has improved on the one hand the activity of Ti element, has then reduced the fusing point of solder on the other hand, has improved intensity under the high-temperature structural ceramics joint hot environment of solder brazing.
The specific embodiment two: what present embodiment and the specific embodiment one were different is: described Co-Ti-Nb is the high temperature active solder according to mass fraction is to be made by the titanium of 16.2 parts of niobiums, 46.2 parts of cobalts and 37.6 parts.Other are identical with the specific embodiment one.
The specific embodiment three: what present embodiment was different with the specific embodiment one or two is: described Co-Ti-Nb is the high temperature active solder according to mass fraction is to be made by the titanium of 23.5 parts of niobiums, 42.2 parts of cobalts and 34.3 parts.Other are identical with the specific embodiment one or two.
The specific embodiment four: what present embodiment was different with one of specific embodiment one to three is: described Co-Ti-Nb is the high temperature active solder according to mass fraction is to be made by the titanium of 30.3 parts of niobiums, 38.4 parts of cobalts and 31.3 parts.Other steps are identical with one of specific embodiment one to three with parameter.
The specific embodiment five: what present embodiment was different with one of specific embodiment one to four is: described Co-Ti-Nb is the high temperature active solder according to mass fraction is to be made by the titanium of 42.7 parts of niobiums, 31.6 parts of cobalts and 25.7 parts.Other steps are identical with one of specific embodiment one to four with parameter.
The specific embodiment six: what present embodiment was different with one of specific embodiment one to five is: the purity of described cobalt is 99.5%～99.9%; The purity of titanium is 99.5%～99.9%; The purity of niobium is 99.5%～99.9%.Other steps are identical with one of specific embodiment one to five with parameter.
The specific embodiment seven: what present embodiment was different with one of specific embodiment one to six is: described Co-Ti-Nb is that the preparation method of high-temp solder is vacuum induction water-cooled copper crucible smelting process or vacuum arc melting method.Other steps are identical with one of specific embodiment one to six with parameter.
The specific embodiment eight: what present embodiment was different with one of specific embodiment one to seven is: described vacuum arc melting method is: a, press the order that is followed successively by Co piece, Ti piece and Nb piece and place crucible; B, take out crucible vacuum to 10
-1Pa feeds high-purity argon gas then, is evacuated to 10 again
-1Pa; Twice of c, the operation of repetition b step; D, with electric arc each metal derby is carried out melting 4～8 times, thinly slice with the wire electric discharge patterning method, polish flat successively with 200#, 400#, 600# and 800# sand paper successively then, namely finishing Co-Ti-Nb is the preparation of high-temp solder.Other steps are identical with one of specific embodiment one to seven with parameter.
By following verification experimental verification beneficial effect of the present invention:
The preparation method is vacuum arc melting method: a, press the order that is followed successively by Co piece, Ti piece and Nb piece places crucible; B, take out crucible vacuum to 10
-1Pa feeds high-purity argon gas then, is evacuated to 10 again
-1Pa; Twice of c, the operation of repetition b step; D, with electric arc each metal derby is carried out melting 6 times, thinly slice with the wire electric discharge patterning method, polish flat successively with 200#, 400#, 600# and 800# sand paper successively then, namely finishing Co-Ti-Nb is the preparation of high-temp solder.
The preparation method is vacuum arc melting method: a, press the order that is followed successively by Co piece, Ti piece and Nb piece places crucible; B, take out crucible vacuum to 10
-1Pa feeds high-purity argon gas then, is evacuated to 10 again
-1Pa; Twice of c, the operation of repetition b step; D, with electric arc each metal derby is carried out melting 6 times, thinly slice with the wire electric discharge patterning method, polish flat successively with 200#, 400#, 600# and 800# sand paper successively then, namely finishing Co-Ti-Nb is the preparation of high-temp solder.
Adopting the Co-Ti-Nb of this test preparation is that the high temperature active solder carries out soldering, and carries out Mechanics Performance Testing.
Soldering C
f/ SiC composite and metal Nb: grinding process is carried out on mother metal to be welded surface, then the Co-Ti-Nb brazing filler metal is put between two mother metals, form the sandwich-like structure, be incubated 10min down at 1320 ℃ and carry out vacuum brazing.After experiment finishes, the joint microscopic structure that obtains as shown in Figure 6, joint microstructure is complete, no significant defect.Adopt compression shear strength to estimate joint performance, (annotate: joint not is disconnected and metal Nb at first surrenders in the time of 800 ℃ for the gentle 600 ℃ of shear at high temperature intensity in the junction chamber that obtains, yield strength has only about 100MPa) be respectively 187MPa and 222MPa, high-temperature behavior than the normal temperature performance boost 18%.
And adopt identical method for welding, be that solder connects mother metal C with TiCuZrNi
fDuring/SiC-Nb, its joint room temperature shear strength is 124MPa, is 70MPa in the time of 750 ℃.
This result shows that the Co-Ti-Nb brazing filler metal can well connect C
f/ SiC composite and metal Nb, and its joint heat-resisting quantity is good.
The preparation method is vacuum arc melting method: a, press the order that is followed successively by Co piece, Ti piece and Nb piece places crucible; B, take out crucible vacuum to 10
-1Pa feeds high-purity argon gas then, is evacuated to 10 again
-1Pa; Twice of c, the operation of repetition b step; D, with electric arc each metal derby is carried out melting 6 times, thinly slice with the wire electric discharge patterning method, polish flat successively with 200#, 400#, 600# and 800# sand paper successively then, namely finishing Co-Ti-Nb is the preparation of high-temp solder.
The preparation method is vacuum arc melting method: a, press the order that is followed successively by Co piece, Ti piece and Nb piece places crucible; B, take out crucible vacuum to 10
-1Pa feeds high-purity argon gas then, is evacuated to 10 again
-1Pa; Twice of c, the operation of repetition b step; D, with electric arc each metal derby is carried out melting 6 times, thinly slice with the wire electric discharge patterning method, polish flat successively with 200#, 400#, 600# and 800# sand paper successively then, namely finishing Co-Ti-Nb is the preparation of high-temp solder.
Adopting the Co-Ti-Nb of this test preparation is that the high temperature active solder carries out soldering, and carries out Mechanics Performance Testing.
Soldering ZrB
2-SiC structural ceramics: to ZrB
2-SiC mother metal carries out grinding process, then the Co-Ti-Nb brazing filler metal is put between two mother metals, forms the sandwich-like structure, is incubated 10min down at 1320 ℃ and carries out vacuum brazing.Experiment is estimated joint performance with the four-point bending intensity of joint after finishing, and the average four-point bending intensity of normal temperature that obtains joint is 150.5MPa.
And adopt identical method for welding, be that solder connects mother metal ZrB with TiCuZrNi
2During-SiC, its joint room temperature shearing strength is 143.5MPa.
The Co-Ti-Nb of test 1～test 4 preparations be high-temp solder organize microphoto shown in Fig. 1～4, by Fig. 1～4 as can be known, along with increasing of Nb content, black phase TiCo ratio reduces, and grey form and aspect TiCo is with (Nb, Ti) eutectic phase of solid solution then increases.When the mass fraction of Nb is increased to 42.7 parts, has only the grey eutectic phase in its tissue, as shown in Figure 4.
Adopting TG-DTA equipment is that high-temp solder is tested to the Co-Ti-Nb that tests 1～test, 4 preparations, obtains the result as shown in Figure 5, and the beginning fusion temperature of four kinds of solders is all between 1260 ℃ to 1270 ℃.
By test 1～test 4 as can be known, this test is based on Co-50Ti(at%), add the infinitely solid molten Nb element of energy and active element Ti.The adding of active element Nb has improved on the one hand the activity of Ti element, has then reduced the fusing point of solder on the other hand, has improved intensity under the high-temperature structural ceramics joint hot environment of solder brazing.
Claims (8)
1. a Co-Ti-Nb is high-temp solder, it is characterized in that Co-Ti-Nb be the high temperature active solder according to mass fraction is to be made by the titanium of 8.5～45 parts of niobiums, 33～50 parts of cobalts and 22～41.5 parts.
2. a kind of Co-Ti-Nb according to claim 1 is high-temp solder, it is characterized in that described Co-Ti-Nb be the high temperature active solder according to mass fraction is to be made by the titanium of 16.2 parts of niobiums, 46.2 parts of cobalts and 37.6 parts.
3. a kind of Co-Ti-Nb according to claim 1 is high-temp solder, it is characterized in that described Co-Ti-Nb be the high temperature active solder according to mass fraction is to be made by the titanium of 23.5 parts of niobiums, 42.2 parts of cobalts and 34.3 parts.
4. a kind of Co-Ti-Nb according to claim 1 is high-temp solder, it is characterized in that described Co-Ti-Nb be the high temperature active solder according to mass fraction is to be made by the titanium of 30.3 parts of niobiums, 38.4 parts of cobalts and 31.3 parts.
5. a kind of Co-Ti-Nb according to claim 1 is high-temp solder, it is characterized in that described Co-Ti-Nb be the high temperature active solder according to mass fraction is to be made by the titanium of 42.7 parts of niobiums, 31.6 parts of cobalts and 25.7 parts.
6. be high-temp solder according to claim 1,2,3,4 or 5 described a kind of Co-Ti-Nb, the purity that it is characterized in that described cobalt is 99.5%～99.9%; The purity of titanium is 99.5%～99.9%; The purity of niobium is 99.5%～99.9%.
7. be high-temp solder according to claim 1,2,3,4 or 5 described a kind of Co-Ti-Nb, it is characterized in that described Co-Ti-Nb is that the preparation method of high-temp solder is vacuum induction water-cooled copper crucible smelting process or vacuum arc melting method.
8. a kind of Co-Ti-Nb according to claim 7 is high-temp solder, it is characterized in that described vacuum arc melting method is: a, press the order that is followed successively by Co piece, Ti piece and Nb piece and place crucible; B, take out crucible vacuum to 10
-1Pa feeds high-purity argon gas then, is evacuated to 10 again
-1Pa; Twice of c, the operation of repetition b step; D, with electric arc each metal derby is carried out melting 4～8 times, thinly slice with the wire electric discharge patterning method, polish flat successively with 200#, 400#, 600# and 800# sand paper successively then, namely finishing Co-Ti-Nb is the preparation of high-temp solder.
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|---|---|---|---|
| CN201310325159.6A CN103341700B (en) | 2013-07-30 | 2013-07-30 | A kind of Co-Ti-Nb system high-temp solder |
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|---|---|---|---|
| CN201310325159.6A CN103341700B (en) | 2013-07-30 | 2013-07-30 | A kind of Co-Ti-Nb system high-temp solder |
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| CN103341700B CN103341700B (en) | 2015-10-28 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104551442A (en) * | 2015-02-03 | 2015-04-29 | 哈尔滨工业大学 | High-temperature solder of brazing ceramic, ceramic matrix composite and metal as well as preparation method and using method of high-temperature solder |
| CN104722594A (en) * | 2015-03-19 | 2015-06-24 | 河南理工大学 | Manufacturing method of large-width eutectic structure aluminium-based brazing filler metal slices |
| CN105290646A (en) * | 2015-12-08 | 2016-02-03 | 哈尔滨工业大学 | Multi-element high-temperature brazing filler metal |
| CN108381057A (en) * | 2018-01-22 | 2018-08-10 | 北京科技大学 | A kind of preparation and method for welding for being brazed the CoTiNb solders of Nb-Ti high temperature alloys |
| CN108907509A (en) * | 2018-08-15 | 2018-11-30 | 哈尔滨工业大学 | A kind of Zr-Ni solder and its preparation method and application for the soldering of nuclear reactor structure |
| CN110814574A (en) * | 2019-11-21 | 2020-02-21 | 江苏威拉里新材料科技有限公司 | High-temperature brazing filler metal |
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| CN102198569A (en) * | 2011-04-19 | 2011-09-28 | 哈尔滨工业大学 | High-temperature solder for brazing TiAl-based alloy and preparation method thereof |
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| US6586118B2 (en) * | 2001-05-30 | 2003-07-01 | General Electric Company | Bonded niobium silicide and molybdenum silicide composite articles using semi-solid brazes |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104551442A (en) * | 2015-02-03 | 2015-04-29 | 哈尔滨工业大学 | High-temperature solder of brazing ceramic, ceramic matrix composite and metal as well as preparation method and using method of high-temperature solder |
| CN104722594A (en) * | 2015-03-19 | 2015-06-24 | 河南理工大学 | Manufacturing method of large-width eutectic structure aluminium-based brazing filler metal slices |
| CN105290646A (en) * | 2015-12-08 | 2016-02-03 | 哈尔滨工业大学 | Multi-element high-temperature brazing filler metal |
| CN105290646B (en) * | 2015-12-08 | 2017-06-06 | 哈尔滨工业大学 | A kind of polynary high-temp solder |
| CN108381057A (en) * | 2018-01-22 | 2018-08-10 | 北京科技大学 | A kind of preparation and method for welding for being brazed the CoTiNb solders of Nb-Ti high temperature alloys |
| CN108907509A (en) * | 2018-08-15 | 2018-11-30 | 哈尔滨工业大学 | A kind of Zr-Ni solder and its preparation method and application for the soldering of nuclear reactor structure |
| CN108907509B (en) * | 2018-08-15 | 2020-12-29 | 哈尔滨工业大学 | Zr-Ni brazing filler metal for brazing nuclear reactor core structure and preparation method and application thereof |
| CN110814574A (en) * | 2019-11-21 | 2020-02-21 | 江苏威拉里新材料科技有限公司 | High-temperature brazing filler metal |
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