CN101185992A - Manganese based solder containing active element Ti suitable for soldering molybdenum and alloy thereof - Google Patents
Manganese based solder containing active element Ti suitable for soldering molybdenum and alloy thereof Download PDFInfo
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- CN101185992A CN101185992A CNA2007100508080A CN200710050808A CN101185992A CN 101185992 A CN101185992 A CN 101185992A CN A2007100508080 A CNA2007100508080 A CN A2007100508080A CN 200710050808 A CN200710050808 A CN 200710050808A CN 101185992 A CN101185992 A CN 101185992A
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Abstract
The invention provides an active element Ti which is suitable for the brazing welding of molybdenum and an MnNiCoCrCuTi alloy of the alloy of the active element Ti, belonging to a welding technique field. The alloy combinations and weight proportions are as the following: 15.0 to 40.0 percent of Ni, 4.0 to 36.0 percent of Cu, 0 to 16.0 percent of Co, 0 to 13.0 percent of Cr, 0.01 to 2.0 percent of Ti, and rest part is Mn. The solder melting temperature of the invention is from 920 to 1135 DEG C and a brazing welding temperature is from 1000 to 1200 DEG C. The invention is suitable for the identical nature vacuum brazing welding of molybdenum and an alloy of molybdenum and is also suitable for the vacuum brazing welding between molybdenum and molybdenum-alloy and stainless steel of different metals. The small content of the active element Ti leads solder, molybdenum and molybdenum alloy to be well lubricated and sews are thoroughly filled so as to guarantee the completeness of brazing welding joints. After welding, no distinct growth happens to crystal granules of molybdenum and molybdenum alloy basic materials. The accuracy of the component is high, welding lines are thick and joints are fixed. The invention can be stably used between 600 and 800 DEG C.
Description
Technical field
The invention belongs to welding technology field, be specifically related to a kind of manganese based solder MnNiCoCrCuTi alloy that contains active element Ti suitable for soldering molybdenum and alloy thereof.It is applicable to the homogeneity vacuum brazing of molybdenum and alloy thereof, also is applicable to the vacuum brazing between molybdenum and alloy thereof and the stainless steel dissimilar metal.
Background technology
Molybdenum and alloy thereof have good thermal conductivity, electric conductivity, low-expansion coefficient, elevated temperature strength, low-vapor pressure and characteristic such as wear-resistant, can be applied to a lot of fields.Molybdenum and alloy thereof being most widely used in electronic equipment is usually used in making internals, high-performance electronic plug-in unit and heat abstractor, medical treatment electronic equipment, X-ray tube inner member (target, support and heat screen) of illumination and electron tube part, microwave equipment etc.; In aviation and aerospace industry, be usually used in making high temperature resistant member, as the covering of the combustion gas impeller blade of engine, nozzle, space vehicle, flame baffle etc.; In nuclear industry, be usually used in making heat exchanger and supportive grid etc.; In addition, also obtained application in fields such as chemical industry, mold manufacturing industries.
The soldering of molybdenum and alloy thereof is a welding method commonly used in producing.When soldering molybdenum and alloy thereof, the selection of solder depends primarily on the serviceability temperature of molybdenum and alloy components thereof.When operating temperature is lower than 500 ℃, the soldering of molybdenum and alloy thereof can first nickel plating or copper facing on molybdenum and alloy thereof, carry out soldering with common money base or copper base solder again, brazing temperature is usually below 1000 ℃, but plating process complexity, coating easily peels off when soldering, often causes the soldered fitting mechanical property to reduce.Operating temperature is in the time of 500 ℃～800 ℃, the soldering of molybdenum and alloy thereof can adopt manganese base or nickel-based solder to carry out vacuum brazing, brazing temperature is usually at 1000 ℃～1500 ℃, but these two kinds of solders are bad to the wetability of molybdenum and alloy thereof, cause solder to sprawl difficulty at molybdenum and alloy surface thereof, the filling gap is insufficient, can influence the mechanical property of soldered fitting to a certain extent.When operating temperature was higher than 800 ℃, titanium base or other dystectic simple metal solders were adopted in the soldering of molybdenum and alloy thereof usually, carry out vacuum brazing, and brazing temperature is mostly more than 1500 ℃.The employed solder of soldering between molybdenum and alloy thereof and the stainless steel dissimilar metal is more rare, generally adopts PdNi solder alloy and CoPd solder alloy, and brazing temperature is at 1300 ℃～1350 ℃.
In existing soldering tech, the brazing temperature of molybdenum and alloy high-temp member thereof is mostly above 1200 ℃, and the recrystallization temperature interval of molybdenum and alloy thereof is at 1150 ℃～1200 ℃, brazing temperature surpasses recrystallization temperature can cause that molybdenum and alloy grain thereof are grown up and the joint embrittlement, cause joint mechanical property to reduce, and too high also can the making by weldering deformation of members amount of temperature increases, and influences the precision of postwelding member, so be preferably in the following soldering of the recrystallization temperature of molybdenum and alloy thereof.
Therefore, brazing temperature has just caused people's attention at 1000 ℃～1200 ℃ manganese-base alloy solder.Manganese based solder has higher room temperature and elevated temperature strength, and good oxidization resistance energy and decay resistance have good wetability to stainless steel, and do not have tangible corrosion and intergranular and infiltrate phenomenon, weld seam densification after the soldering, soldered fitting is firm.But manganese based solder is bad to the wetability of molybdenum and alloy thereof, can influence the mechanical property of soldered fitting when being used for soldering between molybdenum and alloy thereof and the stainless steel dissimilar metal.
At present, in the prior art of soldering molybdenum and alloy thereof, there are the problems referred to above, are unfavorable for widening the engineering application of molybdenum and alloy components thereof.Therefore, but the middle temperature of exploitation and manufacturing soldering molybdenum and alloy thereof, active solder alloy are of practical significance very much.
Summary of the invention
The purpose of this invention is to provide a kind of manganese based solder MnNiCoCrCuTi alloy that contains active element Ti suitable for soldering molybdenum and alloy thereof, its brazing characteristics to molybdenum and alloy thereof is good.In vacuum environment, under 1000 ℃～1200 ℃ conditions of brazing temperature, the highly reliable soldering of finishing member connects technology.It is applicable to the homogeneity vacuum brazing of molybdenum and alloy thereof, also is applicable to the vacuum brazing between molybdenum and alloy thereof and the stainless steel dissimilar metal.Postwelding member precision height, weld seam densification, joint firmly, can be 600 ℃～800 ℃ stable uses.
The present invention contains the manganese based solder of active element Ti suitable for soldering molybdenum and alloy thereof, it is characterized in that the percentage by weight of alloying element is:
Ni 15.0～40.0%Cu 4.0～36.0%Co 0～16.0%Cr 0～13.0%Ti 0.01～2.0%Mn surplus.
The fusing point of manganese is higher to be 1243 ℃, and bad to the wetability of molybdenum and alloy thereof.Therefore, solder of the present invention also adds some metallic elements that are fit on the matrix of manganese, with the brazing filler metal alloy that obtains to be suitable for.The present invention uses alloying element and their effect to be described below:
Ti: add a spot of active element Ti, can improve the activity of solder, make solder good wetability be arranged, promote the reaction of solder and molybdenum and alloy mother metal thereof, reach the purpose of metallurgical binding to molybdenum and alloy mother metal thereof.Practice of the present invention shows that Ti content is lower than 0.01% and does not reach good wetting effect, and content then can cause increasing of fragility phase in the solder greater than 2.0%, influences the processing characteristics of solder, does not reach the operation technique requirement.Therefore, the present invention determines its addition in solder in 0.01～2.0% scope.
Ni: nickel is as the essential element in the solder, and its effect is the fusing point that reduces solder.According to the Mn-Ni binary alloy phase diagram as can be known, manganese and nickel can form solid solution, and when w (Ni) was 40%, the fusing point of alloy is minimum to be 1005 ℃.Therefore, the present invention limit nickel content in this solder alloy on be limited to 40%.Manganese based solder thinks that exactly the Mn-Ni alloy is a matrix, adds that different alloying element forms.
Cu: according to the Mn-Cu binary alloy phase diagram as can be known, the fusing point effect that copper reduces manganese is remarkable, and copper and manganese can form unlimited solid solution, thereby can improve the cold-forming property of solder.But along with the increase of copper content, the fusing point of solder alloy significantly reduces, and can influence the elevated temperature strength of weld seam.Therefore, the present invention limit copper content in this solder alloy on be limited to 36%.
Cr: add non-oxidizability and corrosion resistance that chromium can improve solder alloy, still along with the increase of chromium content, the fusing point of solder alloy raises.Therefore, the present invention limit chrome content in this solder alloy on be limited to 13%.
Co: add elevated temperature strength and corrosion resistance that cobalt can improve solder alloy, still, can form compound between brittle metal in the solder alloy, influence the processing characteristics of solder alloy along with the increase of cobalt content.Therefore, the present invention limit contain in this solder alloy the cobalt amount on be limited to 16%.
Solder alloy of the present invention is applicable to the homogeneity vacuum brazing of molybdenum and alloy thereof, also is applicable to the vacuum brazing between molybdenum and alloy thereof and the stainless steel dissimilar metal.Owing to adopted technique scheme, the present invention to have following superiority:
1, solder alloy of the present invention is good to the wetability of molybdenum and alloy thereof.Manganese based solder is relatively poor to the wetability of molybdenum and alloy thereof, owing to contain active element Ti in this solder, therefore significantly reduces the angle of wetting of molten solder and molybdenum and alloy thereof, improves solder to being welded the wetability of mother metal.
2, the brazing temperature of solder alloy of the present invention is moderate.920 ℃～1135 ℃ of solder alloy fusion temperatures of the present invention, 1000 ℃～1200 ℃ of brazing temperatures, less demanding to equipment, in middle temperature vacuum brazing furnace commonly used, all can finish soldering, avoided the tendency of growing up of molybdenum and alloy grain thereof, improve the plasticity of soldered fitting, also reduced the too high caused deflection of member Yin Wendu simultaneously, improved the precision of postwelding member.
3, after the use solder alloy soldering of the present invention, the good mechanical properties of soldered fitting.Because Mo and Ni, Mn, Co, Cr all can form solid solution,, can form firm metallurgical binding along with the dissolving and the diffusion of brazing filler metal alloy element in mother metal of mother metal in solder reacts.After the soldering, the crystal grain of mother metal molybdenum and alloy thereof does not have the phenomenon of obviously growing up, weld seam densification (seeing description of drawings for details), joint firmly, can be 600 ℃～800 ℃ stable uses.
Description of drawings
Fig. 1 is for using the weld seam metallographic structure (left side is a stainless steel, and the centre is a weld seam, and the right side is a molybdenum) between active manganese based solder soldering stainless steel of the present invention and the molybdenum dissimilar metal.
The specific embodiment
The present invention is directed to the characteristics of molybdenum and alloy thereof, with Mn is matrix, add Ni, Cu and reduce the solder alloy fusing point, the high-temperature behavior and the resistance to corrosion that add Cr, Co raising solder alloy, add active element Ti and improve the wetability of solder, configure the good active manganese based solder alloy of a kind of processing performance molybdenum and alloy thereof.The composition of this solder alloy is: Ni 15.0～40.0%Cu 4.0～36.0%Co 0～16.0% Cr0～13.0%Ti 0.01～2.0%Mn surplus.Material vacuum induction melting with preparing pours into ingot casting then, through forging, hot rolling, cold rolling after, can make foil and use.
The invention will be further described below in conjunction with example.
Example 1: preparing a kind of composition is Ni 23.0%Cu 5.0%Co 6.0%Ti 0.5%, all the other are the solder alloy of Mn, melting and casting in a vacuum, ingot casting through forging, hot rolling, cold rollingly obtain that a kind of ductility is good, the active preferably manganese based solder sheet material of elevated temperature strength.
When carrying out the homogeneity vacuum brazing of molybdenum, adopt the lap brazing joint, preseting solder sheet in the joint gap, 1120 ℃ of brazing temperatures, vacuum 2～3 * 10 with this solder
-2Pa, insulation 10min.After the soldering, solder fills up the joint gap and form fillet around brazed seam, and being welded mother metal molybdenum crystal grain does not have the phenomenon of obviously growing up, and joint is firm, and the shear strength of weld seam can reach 267MPa.Contain cobalt in this solder, thereby elevated temperature strength is better, can be 650 ℃～750 ℃ stable uses.
Example 2: preparing a kind of composition is Ni 23.0%Cu 5.0%Co 16.0%Ti 1.5%, and all the other are the solder alloy of Mn.When carrying out the homogeneity vacuum brazing of TZM alloy, adopt the lap brazing joint, preseting solder sheet in the joint gap, 1200 ℃ of brazing temperatures, vacuum 2～3 * 10 with this solder
-2Pa, insulation 15min.After the soldering, solder fills up the joint gap and form fillet around brazed seam, and being welded mother metal crystal grain does not have the phenomenon of obviously growing up, and joint is firm, and the shear strength of weld seam can reach 283MPa.Cobalt content is higher in this solder, and is bigger to the elevated temperature strength raising, thereby can be 700 ℃～800 ℃ stable uses.
Example 3: preparing a kind of composition is Ni 35.0%Cr 6.0%Cu13.0%Co 5.0%Ti 1.0%, and all the other are the solder alloy of Mn.With this solder brazing molybdenum and stainless steel, adopt the socket soldered fitting of pipe fitting, 1120 ℃ of brazing temperatures, vacuum 2～3 * 10
-2Pa, insulation 15min, solder are preset at by weldering mother metal molybdenum surface, solder fusing back at the mother metal moistened surface, sprawl, fill weld seam by capillarity.After the soldering, solder fills up the joint gap and form fillet around brazed seam, and being welded mother metal molybdenum crystal grain does not have the phenomenon of obviously growing up, soldering member precision height, and joint is firm, and the shear strength of weld seam can reach 227MPa, can be 600 ℃～700 ℃ stable uses.Add the chromium element in this solder, thereby had the good oxidization resistance energy.
Example 4: preparing a kind of composition is Ni 35.0%Cr 12.0%Cu 13.0%Co 5.0%Ti2.0%, and all the other are the solder alloy of Mn.When carrying out the homogeneity vacuum brazing of molybdenum, adopt the lap brazing joint, preseting solder sheet in the joint gap, 1150 ℃ of brazing temperatures, vacuum 2～3 * 10 with this solder
-2Pa, insulation 10min.After the soldering, solder fills up the joint gap and form fillet around brazed seam, and being welded mother metal molybdenum crystal grain does not have the phenomenon of obviously growing up, and joint is firm, and the shear strength of weld seam can reach 246MPa, can be 600 ℃～700 ℃ stable uses.This solder has improved chrome content, thereby has better antioxygenic property.
Example 5: preparing a kind of composition is Ni 27.0%Cu 20.0%Ti 1.5%, and all the other are the solder alloy of Mn.With this solder brazing molybdenum and stainless steel, adopt the socket soldered fitting of pipe fitting, 1060 ℃ of brazing temperatures, vacuum 2～3 * 10
-2Pa, insulation 15min, solder are preset at by weldering mother metal molybdenum surface, and solder fusing back is filled weld seam at the mother metal moistened surface by capillarity.After the soldering, solder fills up the joint gap and form fillet around brazed seam, and being welded mother metal crystal grain does not have the phenomenon of growing up, soldering member precision height, and joint is firm, and the shear strength of weld seam can reach 203MPa.This solder copper content is higher, thereby fusing point is lower, and brazing temperature is lower.
Example 6: preparing a kind of composition is Ni 22.0%Cu 36%Ti 2.0%, and all the other are the solder alloy of Mn.With this solder brazing molybdenum and stainless steel, adopt the socket soldered fitting of pipe fitting, 1000 ℃ of brazing temperatures, vacuum 2～3 * 10
-2Pa, insulation 15min, solder are preset at by weldering mother metal molybdenum surface, and solder fusing back is filled weld seam at the mother metal moistened surface by capillarity.After the soldering, solder fills up the joint gap and form fillet around brazed seam, and being welded mother metal crystal grain does not have the phenomenon of growing up, soldering member precision height, and joint is firm, and the shear strength of weld seam can reach 186MPa.This solder copper content is higher, and fusing point is lower, thereby brazing temperature can be lower, is suitable for the final stage soldering in the multistage soldering.
Claims (4)
1. manganese-base alloy solder, be added with active element Ti, be specially adapted to the homogeneity vacuum brazing of molybdenum and alloy thereof, the perhaps vacuum brazing between molybdenum and alloy thereof and the stainless steel dissimilar metal is characterized in that the composition of this solder alloy is: (percentage by weight)
Active element Ti Ni Cu Cr Co Mn
0.01～2.0% 15.0～40.0% 4.0～36.0% 0～13.0% 0～16.0% surplus
2. manganese based active solder according to claim 1 is applicable to the high member of soldering work temperature requirement, it is characterized in that this solder alloy composition is:
Active element Ti Ni Cu Co Mn
0.01～2.0% 15.0～30.0% 4.0～20.0% 6.0～16.0% surplus
3. manganese based active solder according to claim 1 is applicable to the demanding member of soldering antioxygenic property, it is characterized in that the composition of this solder alloy is:
Active element Ti Ni Cr Cu Co Mn
0.01～2.0% 20.0～40.0% 5.0～13.0% 4.0～20.0% 3.0～7.0% surplus
4. manganese based active solder according to claim 1 is applicable to the final stage soldering that brazing temperature is lower in the substep soldering and mends pricker, it is characterized in that the composition of this solder alloy is:
Active element Ti Ni Cu Mn
0.01～2.0% 20.0～30.0% 20.0～36.0% surplus
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| Application Number | Priority Date | Filing Date | Title |
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| CN200710050808A CN101185992B (en) | 2007-12-14 | 2007-12-14 | Manganese based solder containing active element Ti suitable for soldering molybdenum and alloy thereof |
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| CN200710050808A CN101185992B (en) | 2007-12-14 | 2007-12-14 | Manganese based solder containing active element Ti suitable for soldering molybdenum and alloy thereof |
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| CN101185992B CN101185992B (en) | 2010-05-19 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101954551A (en) * | 2010-11-02 | 2011-01-26 | 山东大学 | Brazing filler metal and process for welding molybdenum-copper alloy and Austenitic stainless steel |
| CN102009238A (en) * | 2010-10-29 | 2011-04-13 | 宁波江丰电子材料有限公司 | Molybdenum target welding method |
| CN101590574B (en) * | 2009-06-29 | 2011-09-28 | 西安理工大学 | High-entropy alloy brazing filler metal for welding TA2 and 0Cr18Ni9Ti and preparation method thereof |
| CN108015445A (en) * | 2017-12-06 | 2018-05-11 | 中广核研究院有限公司 | Microalloying connection method and microalloying connection structure |
| CN112427833A (en) * | 2020-11-16 | 2021-03-02 | 中机智能装备创新研究院(宁波)有限公司 | Manganese-based flux-cored solder and preparation method and application thereof |
| CN114393344A (en) * | 2021-12-30 | 2022-04-26 | 无锡日月合金材料有限公司 | Brazing filler metal for multistage brazing of electric vacuum device and preparation method thereof |
| CN108015445B (en) * | 2017-12-06 | 2024-05-10 | 中广核研究院有限公司 | Microalloyed connection method and microalloyed connection structure |
Family Cites Families (3)
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| JP3383288B2 (en) * | 1998-09-28 | 2003-03-04 | 住友特殊金属株式会社 | Brazing alloy for stainless steel, brazing structure brazed by the brazing alloy, and brazing material for stainless steel |
| CN1184048C (en) * | 2000-09-20 | 2005-01-12 | 中国科学院金属研究所 | High-strength high-toughness weld wire for hidden arc welding of pressure container |
| CN100496863C (en) * | 2006-08-17 | 2009-06-10 | 贵研铂业股份有限公司 | Nickel alloy high temperature solder |
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- 2007-12-14 CN CN200710050808A patent/CN101185992B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101590574B (en) * | 2009-06-29 | 2011-09-28 | 西安理工大学 | High-entropy alloy brazing filler metal for welding TA2 and 0Cr18Ni9Ti and preparation method thereof |
| CN102009238A (en) * | 2010-10-29 | 2011-04-13 | 宁波江丰电子材料有限公司 | Molybdenum target welding method |
| CN101954551A (en) * | 2010-11-02 | 2011-01-26 | 山东大学 | Brazing filler metal and process for welding molybdenum-copper alloy and Austenitic stainless steel |
| CN101954551B (en) * | 2010-11-02 | 2012-05-23 | 山东大学 | Brazing filler metal and process for welding molybdenum-copper alloy and Austenitic stainless steel |
| CN108015445A (en) * | 2017-12-06 | 2018-05-11 | 中广核研究院有限公司 | Microalloying connection method and microalloying connection structure |
| CN108015445B (en) * | 2017-12-06 | 2024-05-10 | 中广核研究院有限公司 | Microalloyed connection method and microalloyed connection structure |
| CN112427833A (en) * | 2020-11-16 | 2021-03-02 | 中机智能装备创新研究院(宁波)有限公司 | Manganese-based flux-cored solder and preparation method and application thereof |
| CN114393344A (en) * | 2021-12-30 | 2022-04-26 | 无锡日月合金材料有限公司 | Brazing filler metal for multistage brazing of electric vacuum device and preparation method thereof |
| CN114393344B (en) * | 2021-12-30 | 2024-05-14 | 无锡日月合金材料有限公司 | Solder for multistage brazing of electric vacuum device and preparation method thereof |
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Assignee: Chengdu Keningda Materials Co., Ltd. Assignor: Sichuan University Contract record no.: 2011510000087 Denomination of invention: Manganese based solder containing active element Ti suitable for soldering molybdenum and alloy thereof Granted publication date: 20100519 License type: Exclusive License Open date: 20080528 Record date: 20110617 |
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