CN106944741A - Add the microalloying method that Zr improves molybdenum and molybdenum alloy arc-seam weld obdurability - Google Patents
Add the microalloying method that Zr improves molybdenum and molybdenum alloy arc-seam weld obdurability Download PDFInfo
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- CN106944741A CN106944741A CN201710284258.2A CN201710284258A CN106944741A CN 106944741 A CN106944741 A CN 106944741A CN 201710284258 A CN201710284258 A CN 201710284258A CN 106944741 A CN106944741 A CN 106944741A
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/20—Bonding
- B23K26/21—Bonding by welding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K10/00—Welding or cutting by means of a plasma
- B23K10/02—Plasma welding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K15/00—Electron-beam welding or cutting
- B23K15/0046—Welding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/346—Working by laser beam, e.g. welding, cutting or boring in combination with welding or cutting covered by groups B23K5/00 - B23K25/00, e.g. in combination with resistance welding
- B23K26/348—Working by laser beam, e.g. welding, cutting or boring in combination with welding or cutting covered by groups B23K5/00 - B23K25/00, e.g. in combination with resistance welding in combination with arc heating, e.g. TIG [tungsten inert gas], MIG [metal inert gas] or plasma welding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/60—Preliminary treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K9/00—Arc welding or cutting
- B23K9/16—Arc welding or cutting making use of shielding gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K9/00—Arc welding or cutting
- B23K9/235—Preliminary treatment
Abstract
The invention discloses the microalloying method that a kind of addition Zr improves molybdenum and molybdenum alloy arc-seam weld obdurability, comprise the following steps：1) to-be-welded region for treating welding workpiece is pre-processed, wherein, the material of workpiece to be welded is pure molybdenum or molybdenum alloy；2) zirconium layer or zirconium paper tinsel are filled in the joint of workpiece to be welded, is then again assembled workpiece to be welded；3) workpiece to be welded is placed in inert protective atmosphere, then treats the to-be-welded region of welding workpiece and preheated；4) welding heat source is acted at the soldered of workpiece to be welded, complete the fusion welds of workpiece to be welded, the position while welding of welded workpiece is incubated again, then it is being cooled to room temperature, complete the microalloying that addition Zr improves molybdenum and molybdenum alloy arc-seam weld obdurability, this method can eliminate the segregation phenomena of impurity element crystal boundary, while improving the arc-seam weld intensity of molybdenum and molybdenum alloy.
Description
Technical field
The invention belongs to welding technology field, it is related to a kind of addition Zr and improves the micro- of molybdenum and molybdenum alloy arc-seam weld obdurability
Alloyage process.
Background technology
Molybdenum, fusing point is up to 2610 DEG C, and neutron absorption cross-section is small, and thermal coefficient of expansion is low, and heat-conductive characteristic is excellent, high-temperature mechanics
Performance is good, and machinability is good, and when temperature is less than 500 DEG C, molybdenum has good stability in air or water.Above-mentioned advantage causes
Molybdenum has important application in fields such as metallurgy, Aeronautics and Astronautics, nuclear energy, military affairs.However, molybdenum and molybdenum alloy are substantially hard crisp materials
Material, weldability extreme difference.Because the fusing point of molybdenum is too high, typically must process preparation by the way of powder metallurgy, material air content compared with
It is high；Meanwhile, molybdenum is very sensitive to impurity such as O, N, C at high temperature, when particularly being solidified in fusion welding molten bath, the impurity such as O, N, C
Element makes arc-seam weld intensity extreme difference easily in grain boundaries segregation.Above mentioned problem seriously constrains molybdenum and molybdenum alloy in structural material
The application in field.
The content of the invention
It is an object of the invention to the shortcoming for overcoming above-mentioned prior art, there is provided one kind addition Zr raising molybdenums and molybdenum alloy
The microalloying method of arc-seam weld obdurability, this method can eliminate the segregation phenomena of impurity element crystal boundary, while improving molybdenum
With the arc-seam weld intensity of molybdenum alloy.
To reach above-mentioned purpose, addition Zr of the present invention improves the microalloy of molybdenum and molybdenum alloy arc-seam weld obdurability
Change method comprises the following steps：
1) to-be-welded region for treating welding workpiece is pre-processed, wherein, the material of workpiece to be welded is pure molybdenum or molybdenum
Alloy；
2) zirconium layer or zirconium paper tinsel are filled in the joint of workpiece to be welded, is then again assembled workpiece to be welded；
3) workpiece to be welded is placed in inert protective atmosphere, then treats the to-be-welded region of welding workpiece and preheated；
4) welding heat source is acted at the soldered of workpiece to be welded, completes the fusion welds of workpiece to be welded, then it is right
The position while welding of welded workpiece is incubated, and is then being cooled to room temperature, is completed addition Zr and is improved molybdenum and molybdenum alloy melting welding weldering
Stitch the microalloying of obdurability.
Step 1) in treat the concrete operations that the to-be-welded region surface of welding workpiece pre-processed and be：Treated with sand paper
The to-be-welded region of welding workpiece is polished, then is treated with sodium hydroxide solution the to-be-welded region of welding workpiece and carried out alkali
Wash, and be rinsed with clear water, then the to-be-welded region of workpiece to be welded is dipped in acetone and is cleaned by ultrasonic, then is blown
It is dry.
Step 4) in welding heat source is acted at the soldered of workpiece to be welded, then using Laser Welding, laser-arc
Combined Welding, electron beam weldering, beam-plasma weldering or argon arc welding complete the fusion welds of workpiece to be welded.
Molybdenum alloy is that molybdenum alloy of the alloying element content less than or equal to 2wt% or the second phase dopant content are less than or equal to
2wt% molybdenum alloy.
The weld seam form of welded workpiece is butt weld or corner connection weld seam.
Step 2) in workpiece to be welded is assembled, make workpiece to be welded joint gap be less than or equal to it is to be welded
The 4% of thickness of workpiece, and the unfitness of butt joint of workpiece joint to be welded is less than or equal to the 4% of thickness of workpiece to be welded.
The mass percent of the zr element mixed in postwelding weld metal be 0.1%, and postwelding weld metal in mixed
The concentration of the zr element entered is 0.08wt%-0.12wt%.
Zirconium layer and the purity of zirconium paper tinsel are more than or equal to 99.99%；
The inert gas is the argon gas that purity is more than or equal to 99.999%.
Zirconium layer is filled in the joint of workpiece to be welded using the method for sputter coating, plating, cold spraying or laser melting coating.
Step 3) in preheating preheating temperature be 450-550 DEG C.
The invention has the advantages that：
Addition Zr of the present invention improves molybdenum and the microalloying method of molybdenum alloy arc-seam weld obdurability is specifically being grasped
When making, zirconium layer or zirconium paper tinsel first are filled in the joint of workpiece to be welded, the stretching for improving pure molybdenum and molybdenum alloy by zirconium is slight
And microscopic structure, wherein, zirconium is larger relative to the size factor of molybdenum, therefore Mo-Zr system solubility is limited, only when temperature reaches
Obvious diffusion just occurs to more than 1300 DEG C, when high-temperature soldering is sintered, zirconium is slowly entered in workpiece to be welded, so that
The tensile strength of weld seam is improved, while affinity of the zirconium at high temperature to oxygen is extremely strong, therefore most of zr element can be with oxygen etc.
Impurity element is combined, and effectively eliminates the segregation phenomena that impurity element is produced in crystal boundary, it is to avoid occur boundary segregation phenomenon, while instead
The ZrO that should be generated2The effect of second phase particles dispersion-strengtherning can be organized to weld seam again.Through experiment, when being not added with Zr, weld seam is brilliant
Boundary's intensity severe weakness, weld seam fracture is intergranular crack pattern during room temperature tensile, and there are a large amount of large scale gas hole defects；Plus
After appropriate Zr, the region that grain boundary fracture occurs for commissure during room temperature tensile is substantially reduced, and transgranular fracture pattern, Er Qie great occurs
Size gas hole defect is substantially reduced, and the arc-seam weld intensity of molybdenum and molybdenum alloy is significantly improved.
Brief description of the drawings
Fig. 1 is flow chart of the invention；
Fig. 2 (a) is the dimensional drawing of the molybdenum alloy light-wall pipe of embodiment one；
Fig. 2 (b) is the dimensional drawing of zirconium paper tinsel annular gasket in embodiment one；
Fig. 2 (c) is the dimensional drawing of molybdenum alloy end plug in embodiment one；
Fig. 3 is welding point and seam center figure in embodiment one；
Fig. 4 is in embodiment one plus Zr and is not added with the stress strain curve figure of molybdenum alloy laser welding head during Zr；
Fig. 5 (a) be embodiment one in be not added with molybdenum alloy laser welding head stretching fracture microstructure during Zr；
Molybdenum alloy laser welding head stretching fracture microstructure figure when Fig. 5 (b) is adds Zr.
Embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings：
Addition Zr of the present invention improves the microalloying method of molybdenum and molybdenum alloy arc-seam weld obdurability including following
Step：
1) to-be-welded region for treating welding workpiece is pre-processed, wherein, the material of workpiece to be welded is pure molybdenum or molybdenum
Alloy；
2) zirconium layer or zirconium paper tinsel are filled in the joint of workpiece to be welded, is then again assembled workpiece to be welded；
3) workpiece to be welded is placed in inert protective atmosphere, then treats the to-be-welded region of welding workpiece and preheated；
4) welding heat source is acted at the soldered of workpiece to be welded, completes the fusion welds of workpiece to be welded, then it is right
The position while welding of welded workpiece is incubated, and is then being cooled to room temperature, is completed addition Zr and is improved molybdenum and molybdenum alloy melting welding weldering
Stitch the microalloying of obdurability.
Step 1) in treat the concrete operations that the to-be-welded region surface of welding workpiece pre-processed and be：Treated with sand paper
The to-be-welded region of welding workpiece is polished, then is treated with sodium hydroxide solution the to-be-welded region of welding workpiece and carried out alkali
Wash, and be rinsed with clear water, then the to-be-welded region of workpiece to be welded is dipped in acetone and is cleaned by ultrasonic, then is blown
It is dry.
Step 4) in welding heat source is acted at the soldered of workpiece to be welded, then using Laser Welding, laser-arc
Combined Welding, electron beam weldering, beam-plasma weldering or argon arc welding complete the fusion welds of workpiece to be welded.
Molybdenum alloy is that molybdenum alloy of the alloying element content less than or equal to 2wt% or the second phase dopant content are less than or equal to
2wt% molybdenum alloy.
The weld seam form of welded workpiece is butt weld or corner connection weld seam.
Step 2) in workpiece to be welded is assembled, make workpiece to be welded joint gap be less than or equal to it is to be welded
The 4% of thickness of workpiece, and the unfitness of butt joint of workpiece joint to be welded is less than or equal to the 4% of thickness of workpiece to be welded.
The mass percent of the zr element mixed in postwelding weld metal is institute in 0.1wt%, and postwelding weld metal
The concentration of the zr element of incorporation is 0.08wt%-0.12wt%.
Zirconium layer and the purity of zirconium paper tinsel are more than or equal to 99.99%；
The inert gas is the argon gas that purity is more than or equal to 99.999%.
Zirconium layer is filled in the joint of workpiece to be welded using the method for sputter coating, plating, cold spraying or laser melting coating.
Step 3) in preheating preheating temperature be 450-550 DEG C.
Embodiment one
With containing 0.25wt%La2O3Exemplified by the docking laser weldering of high-performance molybdenum alloy thin-wall pipe-end plug of dispersion-strengtherning phase,
Primary operational flow in welding process uses 240#, 600#, 1000# successively as shown in figure 1, molybdenum tube and end plug first are docked into region
Sand paper is polished, and is then carried out alkali cleaning with sodium hydrate aqueous solution, is finally cleaned by ultrasonic with acetone, is dried up standby；By thickness
External diameter 10mm, internal diameter 8.5mm annular gasket are processed into for 0.05mm zirconium paper tinsel, with the HNO by 12mL3With 6mL HF+82mL
H2The solution that O is formulated carries out pickling, to remove the oxide-film on zirconium paper tinsel surface, is finally cleaned by ultrasonic with acetone, and drying is standby,
Molybdenum tube, end plug, the shape of zirconium paper tinsel annular gasket and size such as Fig. 2 (a), Fig. 2 (b) and Fig. 2 (c) are shown；Molybdenum tube and end plug are entered
Luggage is matched somebody with somebody, and zirconium paper tinsel annular gasket is filled in both seam crossings, it is ensured that three's fitting tight；The sample to be welded assembled is placed in height
In pure argon protective atmosphere, then butt joint heated, after the temperature of butt joint reaches 500 DEG C, allow power to be 1200kW
Laser beam be irradiated in the seam crossing of molybdenum tube and end plug, sample is rotated a circle with 0.2m/min linear velocity, complete to molybdenum tube and
The Laser Welding boxing of end plug；Postwelding is incubated 30s by welding point more than 500 DEG C, is slowly cooled to room temperature again afterwards, sample weldering
Slit looks are as shown in Figure 3.
A molybdenum tube and end plug joint are welded according to above-mentioned steps and is not added with the sample of zirconium paper tinsel as control, by high-performance molybdenum
Alloy thin-wall pipe mother metal, be not added with zirconium paper tinsel and add zirconium paper tinsel two kinds of high-performance molybdenum Alloy by Laser Welding banjo fixing butt jointings stretched, stretching
Curve is as shown in figure 4, the tensile strength of molybdenum tube mother metal is 720MPa, and elongation reaches 10.6mm during fracture；It is not added with the welding of zirconium paper tinsel
The tensile strength of joint only has 124MPa, and elongation is only 0.52mm during fracture；Plus the tensile strength of zirconium paper tinsel welding point is
480MPa, reaches the 66.7% of mother metal tensile strength, is about not added with 4 times of joint tensile strength during zirconium intermediate layer, is moulded during stretching
Toughness significantly improves compared to when being not added with zirconium paper tinsel, and elongation is 1.54mm during fracture；Fig. 5 (a) and Fig. 5 (b) is two kinds of welderings
The fracture apperance of joint, it can be seen that joint is all broken in commissure when being not added with zirconium paper tinsel, fracture mode is disconnected along crystalline substance
The region of joint about 60% is broken in mother metal when splitting, and adding zirconium paper tinsel, and 40% region is broken in weld seam, and edge occurs for commissure
The region of crystalline substance fracture is substantially reduced, and occurs in that transgranular fracture pattern；Therefore by Mo-0.25La high-performance molybdenum alloy thin-wall pipes
The method that molybdenum foil annular gasket is filled with end plug joint, can significantly improve the toughness of its laser welding head, improve its tension
Intensity.
Claims (10)
1. a kind of addition Zr improves the microalloying method of molybdenum and molybdenum alloy arc-seam weld obdurability, it is characterised in that including with
Lower step：
1) to-be-welded region for treating welding workpiece is pre-processed, wherein, the material of workpiece to be welded is pure molybdenum or molybdenum alloy；
2) zirconium layer or zirconium paper tinsel are filled in the joint of workpiece to be welded, is then again assembled workpiece to be welded；
3) workpiece to be welded is placed in inert protective atmosphere, then treats the to-be-welded region of welding workpiece and preheated；
4) welding heat source is acted at the soldered of workpiece to be welded, completes the fusion welds of workpiece to be welded, then to welding
The position while welding of workpiece is incubated afterwards, is subsequently cooled to room temperature, completes addition Zr raising molybdenums and molybdenum alloy arc-seam weld is tough
The microalloying of property.
2. addition Zr according to claim 1 improves the microalloying method of molybdenum and molybdenum alloy arc-seam weld obdurability, its
Be characterised by, step 1) in treat the concrete operations that the to-be-welded region surface of welding workpiece pre-processed and be：With sand paper pair
The to-be-welded region of workpiece to be welded is polished, then is treated with sodium hydroxide solution the to-be-welded region of welding workpiece and carried out alkali
Wash, and be rinsed with clear water, then the to-be-welded region of workpiece to be welded is dipped in acetone and is cleaned by ultrasonic, then is blown
It is dry.
3. addition Zr according to claim 1 improves the microalloying method of molybdenum and molybdenum alloy arc-seam weld obdurability, its
Be characterised by, step 4) in welding heat source is acted at the soldered of workpiece to be welded, then using Laser Welding, laser-arc
Combined Welding, electron beam weldering, beam-plasma weldering or argon arc welding complete the fusion welds of workpiece to be welded.
4. addition Zr according to claim 1 improves the microalloying method of molybdenum and molybdenum alloy arc-seam weld obdurability, its
It is characterised by, molybdenum alloy is that molybdenum alloy of the alloying element content less than or equal to 2wt% or the second phase dopant content are less than or equal to
2wt% molybdenum alloy.
5. addition Zr according to claim 1 improves the microalloying method of molybdenum and molybdenum alloy arc-seam weld obdurability, its
It is characterised by, the weld seam form of welded workpiece is butt weld or corner connection weld seam.
6. addition Zr according to claim 1 improves the microalloying method of molybdenum and molybdenum alloy arc-seam weld obdurability, its
Be characterised by, step 2) in workpiece to be welded is assembled, make workpiece to be welded joint gap be less than or equal to it is to be welded
The 4% of thickness of workpiece is connect, and the unfitness of butt joint of workpiece joint to be welded is less than or equal to the 4% of thickness of workpiece to be welded.
7. addition Zr according to claim 1 improves the microalloying method of molybdenum and molybdenum alloy arc-seam weld obdurability, its
It is characterised by, the mass percent of the zr element mixed in postwelding weld metal is to be mixed in 0.1%, and postwelding weld metal
The concentration of the zr element entered is 0.08wt%-0.12wt%.
8. addition Zr according to claim 1 improves the microalloying method of molybdenum and molybdenum alloy arc-seam weld obdurability, its
It is characterised by, the purity of zirconium layer and zirconium paper tinsel is more than or equal to 99.99%；
The inert gas is the argon gas that purity is more than or equal to 99.999%.
9. addition Zr according to claim 1 improves the microalloying method of molybdenum and molybdenum alloy arc-seam weld obdurability, its
It is characterised by, zirconium is filled in the joint of workpiece to be welded using the method for sputter coating, plating, cold spraying or laser melting coating
Layer.
10. addition Zr according to claim 1 improves the microalloying method of molybdenum and molybdenum alloy arc-seam weld obdurability, its
Be characterised by, step 3) in preheating preheating temperature be 450-550 DEG C.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107649796A (en) * | 2017-10-10 | 2018-02-02 | 哈尔滨工业大学（威海） | A kind of molybdenum alloy electron beam welding special filling material |
| CN107775194A (en) * | 2017-10-16 | 2018-03-09 | 北京煜鼎增材制造研究院有限公司 | A kind of laser gain material manufacture extension and electron beam welding composite connecting method |
| 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 |
| CN112222614A (en) * | 2020-08-27 | 2021-01-15 | 西安交通大学 | Method for improving molybdenum and molybdenum alloy laser welding head in nitrogen alloying mode |
| CN112222615A (en) * | 2020-08-28 | 2021-01-15 | 西安交通大学 | Method for improving weldability of molybdenum and molybdenum alloy through nitriding |
| CN113039029A (en) * | 2018-11-19 | 2021-06-25 | 普兰西股份有限公司 | Refractory metal component produced by additive method, additive method and powder |
| CN113732505A (en) * | 2021-09-18 | 2021-12-03 | 西安交通大学 | Method for strengthening welding performance of tungsten/molybdenum and alloy thereof by rhenium element |
| 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 |
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| CN112222615B (en) * | 2020-08-28 | 2022-04-05 | 西安交通大学 | Method for improving weldability of molybdenum and molybdenum alloy through nitriding |
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