CN103614593A - Heat-resistant alloy with favorable hot workability and preparation method thereof - Google Patents
Heat-resistant alloy with favorable hot workability and preparation method thereof Download PDFInfo
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- CN103614593A CN103614593A CN201310661039.3A CN201310661039A CN103614593A CN 103614593 A CN103614593 A CN 103614593A CN 201310661039 A CN201310661039 A CN 201310661039A CN 103614593 A CN103614593 A CN 103614593A
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Abstract
The invention relates to a heat-resistant alloy with favorable hot workability and a preparation method thereof, belonging to the technical field of hot working of heat-resistant alloys. The heat-resistant alloy suitable for 700 DEG C supersupercritical thermal power generator set large-caliber boiler tubes comprises the following components in percentage by weight: 21-23% of Cr, at most 1.0% of Fe, 0.05-0.08% of C, at most 0.3% of Mn, at most 0.1% of Si, 11-13% of Co, at most 0.15% of Cu, 8.0-10.0% of Mo, 0.3-0.5% of Ti, 0.8-1.3% of Al, less than 0.010% of P, less than 0.008% of S, 0.002-0.005% of B, at most 1.0% of Nb, at most 0.015% of N, 0.0035-0.016% of Mg, at most 0.6% of V and the balance of nickel and impurities. The preparation method comprises the following steps: charging metal nickel, metal chromium, metal cobalt, ferroniobium and ferrovanadium in an induction furnace crucible, heating until the materials are completely molten, adjusting the temperature, refining for 10-20 minutes, adding electrolytic aluminum and sponge titanium, stirring, and adding ferroboron; after the aluminum, titanium and boron alloy are molten, cooling to 1450-1470 DEG C, charging argon into the furnace while controlling the argon pressure at 2.3-2.6*10<4>Pa, adding magnesium in the form of a 10-20% nickel-magnesium interalloy, keeping for 3-10 minutes, stirring, tapping, and pouring into an ingot. The method enhances the operability of the hot working technique for hot extrusion tubes.
Description
Technical field
The invention belongs to refractory alloy technical field of hot working, particularly relate to a kind of refractory alloy with good thermal processability energy and preparation method thereof, be applicable to the manufacture of the advanced ultra supercritical fired power generating unit of 700 ℃ of steam parameters heavy caliber thick wall associated conduit.
Background technology
At present, generally the unit steam parameter of operation is 31MPa/593 ℃/593 ℃/593 ℃, thermo-efficiency 35% (HHV), and for further improving power plant efficiency, save energy consumption, reduces CO
2deng gas purging, just need further to improve steam parameter.In the steam parameter of power station, comprise temperature and pressure.Research shows, the raising of temperature can obviously improve the thermo-efficiency of power station unit.
Heat-stable material is to restrict fired power generating unit to the main bottleneck problem that more high-parameters develops, and heavy caliber boi1er tube and header are " bottleneck problems in bottleneck ".Vapor temperature in 700 ℃ of steam parameter ultra supercritical thermal power unit boilers is to be progressively warmed up to 700 ℃, and each temperature section all needs to have the candidate's heat-stable material that meets service requirements.Research shows, P92 type martensite heat-resistant steel can be used for the manufacture of the 620 ℃ of following part heavy caliber of vapor temperature boi1er tubes; The G115 new steel grade of people's research and development such as Iron and Steel Research Geueral Inst Liu Zhengdong can be used for the manufacture of 620 ℃ of-650 ℃ of vapor temperature heavy caliber boi1er tubes; And the candidate material of 650 ℃-700 ℃ vapor temperature section heavy caliber boi1er tubes must be used Refractoloy.Research shows, CCA617 Refractoloy can be used for 650 ℃-700 ℃ vapor temperature section heavy caliber boi1er tube materials.
The prototype of CCA617 alloy is the Inconel617 alloy that people often mention, a kind of by solution strengthening and carbide reinforced type Refractoloys such as Co, Mo, the solid solution element of high-content provides very high resistance to deformation, therefore needs the more heat-processing equipment of high pressure.CCA617 alloy is produced heavy caliber thick wall boi1er tube and uses field thermal processing method obviously different from before it: use hot extrusion molding mode to manufacture heavy caliber thick wall boi1er tube.CCA617 Refractoloy process plastic is poor, and hot processing temperature window ranges is 1050～1190 ℃, and hot processing temperature range window is very narrow.During extruding, carry out gross distortion meeting and in blank, store larger heat energy, while making to push, blank temperature raises, if temperature rise amplitude is greater than temperature drop amplitude, blank temperature is during higher than 1200 ℃, can make the fusing of alloy grain boundaries low melting component, the hot workability of infringement alloy, causes product cracking when serious; If blank temperature is lower than 1050 ℃, resistance to deformation sharply raises, grievous injury extrusion equipment and minimizing Life of Die for Extruding Aluminium Alloy.The hot ductility curve of prior art CCA617 alloy homogenizing diffusion annealing state as shown in Figure 1.Narrow hot processing temperature window ranges is brought very big difficulty to the insulation of CCA617 alloy extrusion process blank, product surface quality, execute-in-place technique etc., makes the manufacture of CCA617 alloy heavy caliber thick wall boi1er tube more difficult.
CN103080346A discloses a kind of nickel-base alloy for technical fields such as steam turbine, power station construction, comprises by weight percentage: carbon 0.05 to 0.08%, chromium 21 to 23%; Iron 0.05 to 1.5%; Manganese reaches 0.5%; Silicon reaches 0.25%; Cobalt 11 to 13%; Molybdenum 8.0 to 10.0%; Titanium 0.3 to 0.5%; Aluminium 0.8 to 1.3%; Copper reaches 0.15%; Phosphorus reaches 0.012%; Sulphur reaches 0.008%; Boron > 0.002 and < 0.005%; Niobium reaches 0-1.0%; Nitrogen reaches 0.015%; Magnesium reaches 0.025%; Calcium reaches 0.01%; Vanadium reaches 0.6%; Nickel is the impurity that surplus and smelting cause.In this patent working example Multiple components, not containing Mg element, do not relate to the hot workability of this alloy yet.
Magnesium elements is a kind of element along grain boundary segregation, is not to separate out Mg phase form to exist, and can play the effect that purifies crystal boundary.In Refractoloy, add a small amount of Mg element to mainly contain the impact of two effect: a.Mg on crystal boundary characteristic: it can reduce crystal boundary vacancy concentration, thereby reduce Boundary diffusion coefficient, improve grain boundary carbide form simultaneously; B.Mg can obviously put forward heavy alloyed hot workability, its major cause is because impurity element in Mg element and alloy (element such as S, P) avidity is large, can generate dystectic stable compound, eliminate low melting component at the harmful effect of grain boundaries, improve hot-work ceiling temperature, and then improve the hot workability of refractory alloy.Research shows, magnesium and Sulfur capacity easily form high melting compound MgS, and its fusing point is greater than 2000 ℃.
Yet in each nickel-base alloy all there is an optimum content scope in the good effect of Mg element.Within the scope of best Mg content, the above-mentioned advantageous effect of magnesium elements competence exertion, particularly puies forward heavy alloyed hot workability; When lower than best Mg content scope, the advantageous effect of magnesium can not be given full play to; If higher than best Mg content scope, magnesium elements alloy hot workability has deleterious effects.
Summary of the invention
The object of the present invention is to provide a kind of refractory alloy with good thermal processability and preparation method thereof, by the optimal components scope of Mg element in interpolation and optimized alloy, expanded the hot processing temperature window ranges of refractory alloy, improve the hot workability of this refractory alloy, for obtaining qualified product, provide safeguard.Be applicable to the associated conduit refractory alloy such as heavy caliber boi1er tube, header of advanced ultra supercritical fired power generating unit.
The present invention adds and optimizes magnesium elements optimum content scope, utilizes " Mg is metallurgical " to expand refractory alloy hot processing temperature window ranges of the present invention, improves refractory alloy hot workability of the present invention.Be applicable to 700 ℃ of ultra supercritical fired power generating unit heavy calibers for boi1er tube refractory alloy chemical composition (% by weight) be:
Cr21～23%; Fe≤1.0%; C0.05～0.08%; Mn≤0.3%; Si≤0.1%; Co11～13%; Cu≤0.15%; Mo8.0～10.0%; Ti0.3～0.5%; Al0.8～1.3%; P < 0.010%; S < 0.008%; B0.002～0.005%; Nb≤1.0%; N≤0.015%; Mg0.0035～0.016%; V≤0.6%; Surplus is nickel and inevitable impurity element.
Refractory alloy preparation method of the present invention is as follows:
Adopt existing vacuum induction furnace smelting technology: metallic nickel, chromium metal, cobalt metal, ferro-niobium, vanadium iron are loaded in crucible induction furnace, by being heated to whole fusings, adjust temperature refining and after 10～20 minutes, add electrolytic aluminum and titanium sponge, stir, add ferro-boron, after aluminium, titanium, boron alloy fusing, be cooled to 1450～1470 ℃, in stove, be filled with argon gas, argon pressure is controlled at 2.3 * 10
4pa～2.6 * 10
4pa, magnesium adds with the form of nickel-magnesium master alloy of 10～20%, tapping after keeping stirring for 3～10 minutes, casting ingot-forming, detects each weight percentages of components whether within the scope of internal control.
The control principle of magnesium recovery rate:
The volatilization of element and its vapour pressure are closely related.Under certain condition, the element evaporation loss that vapour pressure is higher is larger, and pure element magnesium approximate vapour pressure in the time of 1600 ℃ is greater than 10
5pa, so magnesium volatility under vacuum is very strong, therefore directly adopts magnesium elements very low as additive recovery rate, and is difficult to control.In order to stablize the recovery rate of magnesium and being uniformly distributed in alloy, conventionally adopt the form of nickel-magnesium master alloy to add, generally adopt the standard lumpiness of 20 * 30mm and nickel-magnesium alloy recovery rate of certain Mg content more stable.
In smelting process, the factor that affects magnesium recovery rate is complicated.The first kind is the composition that has nickel-magnesium alloy that can accurately control in smelting, and the lumpiness of nickel-magnesium alloy added after nickel-magnesium alloy apart from the tapping time, turned over the factors such as the amount of allocating into of stove speed and magnesium.Equations of The Second Kind is the molten steel temperature while adding nickel-magnesium alloy and is filled with the argon pressure in stove.
Under certain vacuum degree, regularly, the argon pressure being filled with in stove is higher for the time of the liquid steel temperature while adding nickel-magnesium alloy, distance tapping and the conditions such as Mg content in nickel-magnesium alloy one, and the recovery rate of magnesium is higher.Research shows, when vacuum induction is smelted, is filled with argon pressure in stove 2.0 * 10
4pa～2.7 * 10
4during Pa, magnesium recovery rate is more stable.Regularly, the concentration of magnesium in molten steel will reduce gradually along with the growth of the residence time of molten steel in stove for argon pressure in input stove and liquid steel temperature one.Magnesium atom is to the diffusion of liquid-gas phase interface from molten steel, and its rate of diffusion increases with the increase of molten steel temperature, and for obtaining higher more stable recovery rate, while adding nickel-magnesium alloy, molten steel temperature general control is between 1450～1470 ℃.
The present invention adopts prior art, analyzes the relation of magnesium elements recovery rate and each factor when vacuum induction furnace smelting.By controlling above-mentioned principal element, utilize the knowhow of vacuum induction furnace smelting magnesium recovery rate to calculate, therefore utilize prior art to smelt the Mg content of refractory alloy in patent of the present invention.
Refractory alloy of the present invention, its beneficial effect is to put forward heavy alloyed upper limit thermal processing distortion temperature, from 1190 ℃ of the highest texturing temperatures at present, be increased to 1250 ℃ of left and right, expanded the hot processing temperature window of this refractory alloy, thereby improved the hot workability of this alloy, with existing alloy phase comparison, improved the operability of the heat processing technique of hot extrude pressure pipe, more easily produce up-to-standard product.
Accompanying drawing explanation
Fig. 1 is the hot ductility curve of prior art refractory alloy homogenizing annealing state.
Fig. 2 is the different Mg content refractory alloy of the present invention and the contrast of prior art thermoplasticity.
Specific embodiment
Embodiment 1
The present invention adopts 50Kg vacuum induction smelting furnace, and through too much wheel smelting, chemical composition, main technologic parameters are respectively as shown in Table 1 and Table 2.Wherein, in table 1,0# is existing typical technology composition, and 1#～8# is respectively the composition of different Mg content of the present invention.
Table 1 heterogeneity of the present invention
Table 2 the present invention is different, and Mg content is controlled and smelting process parameter
The different Mg content of the present invention to the sex beneficial effect of hot-work as shown in Figure 2.
Claims (3)
1. a refractory alloy with good thermal processability, is characterized in that: alloy composition is counted with % by weight: Cr21～23%; Fe≤1.0%; C0.05～0.08%; Mn≤0.3%; Si≤0.1%; Co11～13%; Cu≤0.15%; Mo8.0～10.0%; Ti0.3～0.5%; Al0.8～1.3%; P < 0.010%; S < 0.008%; B0.002～0.005%; Nb≤1.0%; N≤0.015%; Mg0.0035～0.016%; V≤0.6%; Surplus is nickel and inevitable impurity element.
2. refractory alloy according to claim 1, is characterized in that: this alloy is for the pipeline of 700 ℃ of ultra supercritical fired power generating unit.
3. the preparation method of refractory alloy described in a claim 1 or 2, it is characterized in that: metallic nickel, chromium metal, cobalt metal, ferro-niobium, vanadium iron are loaded in crucible induction furnace, by being heated to whole fusings, adjust temperature refining and after 10～20 minutes, add electrolytic aluminum and titanium sponge, stir, add ferro-boron, after aluminium, titanium, boron alloy fusing, be cooled to 1450～1470 ℃, in stove, be filled with argon gas, argon pressure is controlled at 2.3 * 10
4pa～2.6 * 10
4pa, magnesium adds with the form of nickel-magnesium master alloy of 10～20%, tapping after keeping stirring for 3～10 minutes, casting ingot-forming.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103866163A (en) * | 2014-03-14 | 2014-06-18 | 钢铁研究总院 | Nickel-chromium-cobalt-molybdenum heat resisting alloy and pipe manufacturing process thereof |
| CN104087767A (en) * | 2014-07-08 | 2014-10-08 | 张家港市飞浪泵阀有限公司 | Method for smelting nickel-based alloy by adopting non-vacuum induction furnace |
| CN104099545A (en) * | 2014-07-19 | 2014-10-15 | 太原钢铁(集团)有限公司 | Manufacturing method of nickel-based heat-resisting alloy seamless tube |
| CN105112728A (en) * | 2015-09-29 | 2015-12-02 | 钢铁研究总院 | Heat-resisting alloy for 700-DEG C ultra-supercritical steam turbine rotor and preparation method thereof |
| CN106676331A (en) * | 2016-12-22 | 2017-05-17 | 钢铁研究总院 | High-temperature-resistant high-elastic nickel-chromium alloy strip and preparation method thereof |
| WO2021248755A1 (en) * | 2020-06-12 | 2021-12-16 | 江苏银环精密钢管有限公司 | Novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless pipe for use in power station and manufacturing method therefor |
| CN114921674A (en) * | 2022-05-11 | 2022-08-19 | 重庆材料研究院有限公司 | Vacuum induction melting method of 625 alloy |
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| EP2330225A1 (en) * | 2008-10-02 | 2011-06-08 | Sumitomo Metal Industries, Ltd. | Ni BASED HEAT-RESISTANT ALLOY |
| CN103080346A (en) * | 2010-03-16 | 2013-05-01 | 蒂森克鲁普德国联合金属制造有限公司 | Nickel-chromium-cobalt-molybdenum alloy |
| CN103276251A (en) * | 2013-05-29 | 2013-09-04 | 钢铁研究总院 | Boiler tube for 700 DEG C steam parameter thermal power generating unit and preparation method thereof |
| CN103361518A (en) * | 2013-06-11 | 2013-10-23 | 太原钢铁(集团)有限公司 | Nickel-based seamless pipe for ultra supercritical boiler and manufacturing method thereof |
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Patent Citations (4)
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| EP2330225A1 (en) * | 2008-10-02 | 2011-06-08 | Sumitomo Metal Industries, Ltd. | Ni BASED HEAT-RESISTANT ALLOY |
| CN103080346A (en) * | 2010-03-16 | 2013-05-01 | 蒂森克鲁普德国联合金属制造有限公司 | Nickel-chromium-cobalt-molybdenum alloy |
| CN103276251A (en) * | 2013-05-29 | 2013-09-04 | 钢铁研究总院 | Boiler tube for 700 DEG C steam parameter thermal power generating unit and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103866163A (en) * | 2014-03-14 | 2014-06-18 | 钢铁研究总院 | Nickel-chromium-cobalt-molybdenum heat resisting alloy and pipe manufacturing process thereof |
| CN103866163B (en) * | 2014-03-14 | 2016-03-30 | 钢铁研究总院 | A kind of nickel chromium cobalt molybdenum refractory alloy and tubing manufacturing process thereof |
| CN104087767A (en) * | 2014-07-08 | 2014-10-08 | 张家港市飞浪泵阀有限公司 | Method for smelting nickel-based alloy by adopting non-vacuum induction furnace |
| CN104087767B (en) * | 2014-07-08 | 2016-08-24 | 张家港市飞浪泵阀有限公司 | The method of non-vacuum induction furnace melting nickel-base alloy |
| CN104099545A (en) * | 2014-07-19 | 2014-10-15 | 太原钢铁(集团)有限公司 | Manufacturing method of nickel-based heat-resisting alloy seamless tube |
| CN104099545B (en) * | 2014-07-19 | 2016-04-27 | 太原钢铁(集团)有限公司 | A kind of manufacture method of Refractoloy seamless tube |
| CN105112728A (en) * | 2015-09-29 | 2015-12-02 | 钢铁研究总院 | Heat-resisting alloy for 700-DEG C ultra-supercritical steam turbine rotor and preparation method thereof |
| CN106676331A (en) * | 2016-12-22 | 2017-05-17 | 钢铁研究总院 | High-temperature-resistant high-elastic nickel-chromium alloy strip and preparation method thereof |
| CN106676331B (en) * | 2016-12-22 | 2018-10-09 | 钢铁研究总院 | A kind of high-elastic nichrome band of high temperature resistant and preparation method thereof |
| WO2021248755A1 (en) * | 2020-06-12 | 2021-12-16 | 江苏银环精密钢管有限公司 | Novel nickel-chromium-cobalt-molybdenum high-temperature alloy seamless pipe for use in power station and manufacturing method therefor |
| CN114921674A (en) * | 2022-05-11 | 2022-08-19 | 重庆材料研究院有限公司 | Vacuum induction melting method of 625 alloy |
| CN114921674B (en) * | 2022-05-11 | 2023-03-14 | 重庆材料研究院有限公司 | Vacuum induction melting method of 625 alloy |
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