CN105014258A - Nickel-base superalloy welding wire for 700 DEG C-above ultra-supercritical coal power generation equipment - Google Patents
Nickel-base superalloy welding wire for 700 DEG C-above ultra-supercritical coal power generation equipment Download PDFInfo
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- CN105014258A CN105014258A CN201510364544.0A CN201510364544A CN105014258A CN 105014258 A CN105014258 A CN 105014258A CN 201510364544 A CN201510364544 A CN 201510364544A CN 105014258 A CN105014258 A CN 105014258A
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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
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3033—Ni as the principal constituent
- B23K35/304—Ni as the principal constituent with Cr as the next major constituent
-
- 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
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
- B23K35/0261—Rods, electrodes, wires
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
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Abstract
The invention discloses a nickel-base superalloy welding wire for 700 DEG C-above ultra-supercritical coal power generation equipment, and belongs to the technical field of nickel-base superalloys. The nickel-base superalloy welding wire comprises the following chemical components: 0.005-0.08 wt% of C, 22-25 wt% of Cr, 12-22 wt% of Co, 0.5-2.0 wt% of Ti, 1.0-2.5 wt% of Al, 0.5-2.0 wt% of Nb, 0.5-4.5 wt% of Mo, 0.1-3.0 wt% of W, 0.01-0.3 wt% of V, 0.001-0.05 wt% of Zr, no more than 0.02 wt% of Mg, 0.001-0.006 wt% of B, no more than 1.5 wt% of Fe, and the balance Ni and inevitable impurity elements. As such elements as Co, Cr, Mo, W, Al, Ti and Nb and proper amounts of other microelements are added in a nickel-base alloy, the cold/hot machinability, the high-temperature strength and in particular the high-temperature durability of the alloy welding wire are all improved. The alloy welding wire is better in high-temperature strength and durability, and is more excellent in welding process performance; and in the welding process, a molten pool is better in fluidity, and the welding line formability is excellent.
Description
Technical field
The invention belongs to nickel base superalloy technical field, particularly relate to a kind of more than 700 DEG C ultra supercritical coal power generation equipment nickel base superalloy welding wires, be applicable to the advanced ultra supercritical coal powerplant welding manufacture that vapor (steam) temperature is more than 700 DEG C.
Background technology
Material involved in the present invention is the New Nickel based high-temperature alloy welding wire for the manufacture of more than 700 DEG C ultra supercritical coal powerplants.
The energy and environmental problem are focus in development of world economy process and difficult point always, have also become the main restricting factor of world sustainable development simultaneously.At present, coal-fired thermal power generation at overwhelming majority of countries dominate, and from now on quite over a long time in can not change.China is coal production and consumption big country, and wherein coal-fired thermal power generation accounts for the maximum greenhouse gas emission source of about 70% ~ 80%, Mei electricity Shi China of gross generation, be the crucial industry realizing target for energy-saving and emission-reduction, and China's coal fired power generation efficiency is comparatively low.There are some researches show, the generating equipment steam parameter value improving thermal power plant effectively can improve generating efficiency, reduces CO
2discharge capacity, coal-fired and reduction pollutant SOx, NOx and CO to saving
2deng discharge played important function.Therefore many countries are all developing more high efficiency ultra supercritical thermal power generation unit.
The raising of thermoelectricity generating equipment parameter need can under high parameter service condition the material of long-term safety, reliability service.These materials should have enough elevated temperature strengths, high temperature corrosion resistance, chronic tissue stability and good processing performance under high parameter.Several candidate materials for the manufacture of 700 DEG C of ultra supercritical power generation equipment high temperature section comprise: Haynes 230, GH2984, CCA617, Nimonic 263, Inconel 740 and modified alloy Inconel 740H etc. thereof.And these alloys all belong to nickel-base alloy.Because nickel-base alloy has special physical property, as comparatively large in poor fluidity, stickiness and large etc. to impurity sensitiveness, therefore welding performance is poor, easily produces pore, crackle etc.And welding is one of the most key operation in coal powerplant manufacture process, the performance requirement of ultra supercritical coal powerplant to welding position is high simultaneously.Welding position performance depends on solder wire material and welding procedure, and as making the critical material of welding position, must select rational solder wire material.For at present selected 700 DEG C of ultra supercritical power generation equipment high temperature section alloy materials---Inconel 740H alloy, its weldability and property of welded joint to meet the demands etc. and face many challenges.The nickel-base alloy bare welding filler metal introduced in United States Patent (USP) (US 2009/0321405 A1) " high strength and corrosion-resistant Ni-Co-Cr alloy welding wire and manufacture method ", containing boundary-strengthening element such as solution strengthening type element and B, Zr such as less Mo, W in its chemical composition, this soldering wire alloy type belongs to ageing strengthening type.And adopt this patented invention alloy welding wire to weld, find that in seam organization, γ ' stripping section has easily appearred in crystal boundary, and then ageing strengthening effect reduces, and owing to there is not solution strengthening type element, thus its property of welded joint is greatly affected.Meanwhile, the Inconel 740H joint microstructure adopting existing Nimonic 263, Haynes 282 and CCA617 welding wire to weld and performance all can not meet more than 700 DEG C ultra supercritical coal powerplant index requests.
Summary of the invention
The object of the present invention is to provide a kind of more than 700 DEG C ultra supercritical coal powerplant nickel-base alloy bare welding filler metals, Composition Design is reasonable, have that hot-workability is good, high-temperature behavior is good and deposited metal superior performance, simultaneously inner and surface cleanliness advantages of higher.
The chemical composition of more than 700 DEG C ultra supercritical coal powerplant nickel-base alloy bare welding filler metals provided by the invention is: C0.005 ~ 0.08wt%, Cr 22.0 ~ 25.0wt%, Co 12.0 ~ 22.0wt%, Ti 0.5 ~ 2.0wt%, Al 1.0 ~ 2.5wt%, Nb 0.5 ~ 2.0wt%, Mo 0.5 ~ 4.5wt%, W 0.1 ~ 3.0wt%, V 0.01-0.3wt%, Zr 0.001-0.05wt%, Mg≤0.02wt%, B 0.001-0.006wt%, Fe≤1.5wt%, and surplus is Ni and inevitable impurity element.In impurity element, the scope of S, P, Si and Mn is: S≤0.005wt%, P≤0.010wt%, Si 0.01-0.3wt% and Mn≤0.5wt%.
The main alloy element C of nickel base superalloy welding wire of the present invention, Cr, Co, Mo, W, Nb, Ti, Al, B, Zr, Mg, V, the content control range of Ni and inevitable impurity element S, P, Si, Mn etc. is described above.In addition, the content of the strict trace impurity such as control Pb, Sn, As, Sb, Bi.
Alloying component of the present invention adopts following mentality of designing: based on high-temperature comprehensive property good Ni base alloy, adds the important element that Cr, Co etc. put forward heavy alloyed corrosion resistance and elevated temperature strength.Add Al, Ti and Nb element simultaneously, form γ ' hardening constituent with Ni together, to play its precipitation strength effect; Also add a certain amount of Mo and W element, play important solution strengthening effect.Rationally add a certain amount of Mg element, Mg, as a kind of alterant, effectively can change the form of carbide, strip carbide is become graininess simultaneously.Add a certain amount of V, Zr and B element in addition, play its effect, thus improve the mechanical property of alloy.Therefore, how to determine that element contamination is one of feature of the present invention.The reason of each elemental constituent scope restriction of alloy will be set forth below.
The formation of C element content major effect carbide, forms M at crystal boundary
23c
6carbide, forms primary carbide MC simultaneously together with Ti with Nb.Along with C element content improves, M
23c
6carbide and MC carbide start Precipitation Temperature and increase.When C element content is lower, do not become enough M at crystal boundary
23c
6carbide.But be easy to because MC Precipitation Temperature is higher separate out, when thus C content is higher, be easy to too much consume Ti and Nb element.Therefore, C element content is set within the scope of 0.005 ~ 0.08wt%.
Cr element is owing to can form form compact and stable Cr at alloy surface
2o
3oxide-film, thus can significantly improve the antioxygenic property of nickel-base alloy in the high-temperature vapor environment residing for boiler tubing inside and corrosion resistance.Due to carbide can be formed with C element, also play solution strengthening effect simultaneously, thus can put forward heavy alloyed elevated temperature strength.And for alloy of the present invention, when other constituent contents are constant, Cr constituent content higher than 25.0% time, separate out α-Cr phase in alloy, processing characteristics and the mechanical property of alloy are unfavorable.
Co element can improve nickel-base alloy intensity at high temperature and corrosion resistance equally, and for alloy of the present invention, when other constituent contents are constant, when Co constituent content is higher than 22.0wt%, in alloy, same harmful phase η phase of separating out is separated out.Simultaneously for cost consideration, Co constituent content should be limited in 12.0 ~ 22.0wt%.
Ti element is one of important forming element of γ ' hardening constituent, also can form MC carbide with C element simultaneously, thus can be highly beneficial to improving alloy strength and controlling crystallite dimension.But for alloy of the present invention, when other constituent contents are constant, when Ti constituent content is more than 2.0wt%, can promote that the η phase be harmful to is separated out, therefore, Ti constituent content should control within the scope of 0.5 ~ 2.0wt%.
Al element is one of important forming element of γ ' hardening constituent equally, in addition Al element can with the acting in conjunction of Cr element, make alloy at high temperature form fine and close tough and tensile Cr
2o
3and Al
2o
3oxide-film, and then carry heavy alloyed high-temperature oxidation resistance.When Al constituent content is lower than 1.0wt%, strengthening effect is not obvious, has harmful phase η phase simultaneously and separates out.And when its too high levels, the too high alloy processing characteristics that is unfavorable for of strengthening effect, also can cause harmful phase σ phase to be separated out in addition.Therefore, Al constituent content should control at 1.0 ~ 2.5wt%.
Nb element can play precipitation strength and solution strengthening effect simultaneously, forms γ ' hardening constituent together with Al and Ti with Ni.But must control Nb in right amount, when Nb constituent content is lower than 0.5wt%, harmful phase μ phase can be caused to separate out, when content is higher than 2.0wt%, not only can promote the formation of η phase and σ phase, welding performance also can be made to degenerate, easily produce liquation crack in heat affected area.
Mo element and W element are important solution strengthening element, particularly W and Mo and add the solution strengthening effect that plays compound to raising alloy high-temp intensity advantageously simultaneously.And Mo element alloy anti-flue gas corrosion in coal-fired environment is obviously harmful to, and can promote that σ phase is formed, content, more than promoting during 4.5wt% that harmful phase μ phase is separated out, affects the high temperature process of alloy.Too high content of element W alloy resistance to high temperature corrosion performance is harmful to, and meanwhile, can promote the precipitation of σ phase and μ phase harmful phase.Therefore, Mo constituent content controls within the scope of 0.5 ~ 4.5wt%, and content of element W controls within the scope of 0.1 ~ 3.0wt%.
V element can play precipitation strength and solution strengthening effect equally simultaneously.V element easily and C element form the VC of small and dispersed, favourable to refining alloy crystal grain.V element content controls within the scope of 0.01-0.3wt%.
B element and the acting in conjunction of Zr element, all in crystal boundary enrichment, increase Grain-boundary Junctions and make a concerted effort.To putting forward heavy alloyed creep rupture performance clearly, in alloy of the present invention, B element controls between 0.001 ~ 0.006%, and Zr control of element is within the scope of 0.001-0.05wt%.
Mg, as a kind of alterant, effectively can change the form of carbide, strip carbide is become graininess, and then is conducive to improving alloy creep rupture life and plasticity.But owing to forming non-metallic inclusion, its content is unsuitable too high, and Mg constituent content should control at below 0.02wt%.
By adding the elements such as Co, Cr, Mo, W, Al, Ti, Nb and other appropriate trace element in nickel-base alloy, the cold and hot working performance of alloy welding wire, elevated temperature strength especially high temperature endurance performance etc. are all improved.Alloy welding wire of the present invention has good elevated temperature strength and enduring quality, has comparatively excellent welding technological properties simultaneously, in welding process molten bath mobility better, appearance of weld excellent performance.Be applicable to the manufacture of more than 700 DEG C ultra supercritical coal powerplants.
Detailed description of the invention
Technical scheme of the present invention is illustrated below by embodiment.
More than 700 DEG C ultra supercritical coal powerplant nickel base superalloy welding wires, comprise C, Cr, Co, Mo, W, Nb, Ti, Al, B, Zr, Mg, V, Ni and inevitable impurity element, survey the percentage by weight of S, P, Si and Mn in the percentage by weight of each composition and impurity obtained in table 1.
Embodiment alloy composition testing result contrasts as shown in table 1 with external solder wire material chemical composition in kind of developing.
The chemical composition measured result of table 1 embodiment 1-7 alloy and comparative example alloy
More than 700 DEG C ultra supercritical coal powerplant nickel base superalloys in embodiment 1,3,5,7 and comparative example are processed into pole shape tensile sample, carry out the tensile property test of room temperature, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C and 800 DEG C respectively.Erichsen test result is as shown in table 2.
The room temperature of table 2 embodiment and comparative example nickel-base alloy and high temperature tensile properties
Note: all samples are all through the heat treatment of 1150 DEG C/1h water-cooled+800 DEG C/4h air cooling.
Data in contrast table 2 can be found out: during the room temperature tensile of 700 DEG C of grade ultra supercritical coal fired power plant nickel base superalloy welding wires of embodiment, yield strength is greater than 780MPa, tensile strength is greater than 1180MPa, percentage elongation is greater than 30.0%, and shrinkage factor is greater than 40.0%; During 600 DEG C of drawing by high temperature, yield strength is greater than 650MPa, and tensile strength is greater than 1010MPa, and percentage elongation is greater than 30.0%, and shrinkage factor is greater than 40.0%; During 650 DEG C of drawing by high temperature, yield strength is greater than 650MPa, and tensile strength is greater than 1000MPa, and percentage elongation is greater than 25.0%, and shrinkage factor is greater than 40.0%; During 700 DEG C of drawing by high temperature, yield strength is greater than 640MPa, and tensile strength is greater than 900MPa, and percentage elongation is greater than 15.0%, and shrinkage factor is greater than 20.0%; During 750 DEG C of drawing by high temperature, yield strength is greater than 620MPa, and tensile strength is greater than 820MPa, and percentage elongation is greater than 11.0%, and shrinkage factor is greater than 18.0%; During 850 DEG C of drawing by high temperature, yield strength is greater than 600MPa, and tensile strength is greater than 730MPa, and percentage elongation is greater than 11.0%, and shrinkage factor is greater than 15.0%; Room temperature and high temperature tensile properties all have higher intensity and plasticity, and plasticity and toughness are better.
And develop more than 700 DEG C ultra supercritical coal powerplant welding wires nickel-base alloy (comparative example) abroad due to not containing the element such as Mo, W, V, B, Zr, its room temperature and mechanical behavior under high temperature all relatively low.The composition range that the present invention proposes and restrictive condition are that alloy possesses good mechanical property and provides strong guarantee.
High temperature endurance performance is checked:
Embodiment and comparative example alloy are processed into pole shape duration running sample, all samples are all through the heat treatment of 1150 DEG C/1h water-cooled+800 DEG C/4h air cooling.Carry out 750 DEG C, the test of the enduring quality of 379MPa respectively.Its result of the test is as shown in table 3.
Table 3 embodiment and comparative example alloy high-temp enduring quality testing result
| Alloy | Temperature, DEG C | Stress, MPa | Creep rupture life, h | Percentage elongation, % |
| Embodiment 1 | 750 | 379 | 37.3 | 3.4 |
| Embodiment 3 | 750 | 379 | 38.2 | 3.1 |
| Embodiment 5 | 750 | 379 | 44.1 | 4 |
| Embodiment 7 | 750 | 379 | 36.2 | 3.2 |
| Comparative example | 750 | 379 | 23.1 | 2 |
Embodiment of the present invention alloy and comparative example alloy adopt the welding procedure of contract to carry out deposited metal making.And from deposited metal, get high temperature endurance performance test samples, sample has all carried out 800 DEG C/4h air cooling aging strengthening model.Carry out 750 DEG C, the test of the enduring quality of 379MPa respectively.Deposited metal high temperature endurance performance testing result is as shown in table 4.
Table 4 embodiment and comparative example alloy deposited metal high temperature endurance performance testing result
| Alloy | Temperature, DEG C | Stress, MPa | Creep rupture life, h | Percentage elongation, % |
| Embodiment 1 | 750 | 379 | 33.2 | 3 |
| Embodiment 3 | 750 | 379 | 34.2 | 2.8 |
| Embodiment 5 | 750 | 379 | 40.1 | 3.6 |
| Embodiment 7 | 750 | 379 | 33.2 | 2.9 |
| Comparative example | 750 | 379 | 20.5 | 1.8 |
Alloy welding wire of the present invention has good room temperature, elevated temperature strength and enduring quality, and deposited metal high temperature endurance performance is excellent.There is comparatively excellent welding technological properties simultaneously, in welding process molten bath mobility better, appearance of weld excellent performance.Be applicable to the manufacture of more than 700 DEG C ultra supercritical coal powerplants.
Claims (2)
1. one kind more than 700 DEG C ultra supercritical coal power generation equipment nickel base superalloy welding wires, it is characterized in that, studying of this nickel base superalloy welding wire is divided into: C 0.005 ~ 0.08wt%, Cr22 ~ 25wt%, Co 12 ~ 22wt%, Ti 0.5 ~ 2.0wt%, Al 1.0 ~ 2.5wt%, Nb 0.5 ~ 2.0wt%, Mo 0.5 ~ 4.5wt%, W 0.1 ~ 3.0wt%, V 0.01-0.3wt%, Zr 0.001-0.05wt%, Mg≤0.02wt%, B 0.001-0.006wt%, Fe≤1.5wt%, and surplus is Ni and inevitable impurity element.
2. alloy welding wire according to claim 1, is characterized in that, in described impurity element, the scope of S, P, Si and Mn is: S≤0.005wt%, P≤0.010wt%, Si 0.01-0.3wt% and Mn≤0.5wt%.
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