EP3985139A1 - Low-chromium corrosion-resistant high-strength polycrystalline high-temperature alloy and preparation method therefor - Google Patents
Low-chromium corrosion-resistant high-strength polycrystalline high-temperature alloy and preparation method therefor Download PDFInfo
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- EP3985139A1 EP3985139A1 EP20821820.6A EP20821820A EP3985139A1 EP 3985139 A1 EP3985139 A1 EP 3985139A1 EP 20821820 A EP20821820 A EP 20821820A EP 3985139 A1 EP3985139 A1 EP 3985139A1
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- 239000000956 alloy Substances 0.000 title claims abstract description 113
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 112
- 239000011651 chromium Substances 0.000 title claims abstract description 35
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 34
- 238000005260 corrosion Methods 0.000 title claims abstract description 32
- 230000007797 corrosion Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title 1
- 238000010438 heat treatment Methods 0.000 claims abstract description 68
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910000601 superalloy Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 17
- 239000010937 tungsten Substances 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 13
- 239000010955 niobium Substances 0.000 claims abstract description 13
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005098 hot rolling Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims description 60
- 239000012452 mother liquor Substances 0.000 claims description 24
- 238000003723 Smelting Methods 0.000 claims description 18
- 238000001953 recrystallisation Methods 0.000 claims description 9
- 238000005096 rolling process Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000007711 solidification Methods 0.000 claims description 7
- 230000008023 solidification Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000000265 homogenisation Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- 239000000919 ceramic Substances 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 241001062472 Stokellia anisodon Species 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 229910001005 Ni3Al Inorganic materials 0.000 description 3
- 230000003064 anti-oxidating effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004881 precipitation hardening Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910001235 nimonic Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
Images
Classifications
-
- 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
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
Definitions
- the present invention relates to the field of superalloy materials, and more particularly relate to a low-chromium corrosion-resistant high-strength polycrystalline superalloy and a method of preparing the same.
- the superheater/reheater withstands multiple impacts including high-temperature creep, thermal fatigue, oxidation, and high-temperature fireside corrosion, etc. With substantial increase of main steam parameters of the fossil-fired boiler, it is needed to develop a high-temperature alloy material that may satisfy operating performance requirements of a superheater/reheater tube of a high-parameter power unit in the industry of fossil-fired power generation.
- the superheater/reheater as a component having severest service conditions in a fossil-fired boiler is very demanding on creep rupture strength and corrosion-resistant property of a candidate material.
- a variety of nickel-based wrought superalloy materials have been developed abroad, such as Inconel ® 740H developed by Special Metals, Haynes ® 282 developed by Haynes International, CCA 617 developed by Thyssenkrupp, Nimonic 263 developed by Rolls-Royce, FENIX700 developed by Hitachi, TOS1X developed by Toshiba, and LTESR700 developed by Mitsubishi.
- conventional candidate materials generally have a relatively low Al/ Ti ratio.
- the relatively high Cr content in the alloy also ensures its anti-oxidation and anti-corrosion properties.
- the ever-increasing steam parameters of fossil-fired generating units pose more harsh challenge to alloy properties.
- Al Al (Aluminum) is an important element promoting precipitation hardening in the alloy.
- a relatively high Al content facilitates increasing Ni 3 Al volume fraction in the alloy, further conferring a superior strength performance to the alloy.
- addition of the Al element also facilitates formation of Al 2 O 3 , which substantially promotes high-temperature anti-oxidation and anti-corrosion properties of the alloy.
- addition of the Al element also causes structural instability in the alloy; particularly, a relatively high Al content significantly affects the solidification structure of the alloy.
- An object of the present invention is to provide a low-chromium corrosion-resistant high-strength polycrystalline superalloy and a method of preparing the same, wherein by leveraging the characteristics of Al as an element for strengthening Ni 3 Al formation in conjunction with its property of improving anti-corrosion property of the alloy, a critical Al content necessary for ensuring formation of Al 2 O 3 in the oxidation/corrosion process of the alloy is added, and a range of Al content in the alloy is stringently controlled while ensuring structural stability of the alloy, so as to promote precipitation of a considerable amount of homogeneously dispersed, second-phase strengthened particles in the alloy to obtain a desired strength property.
- the present invention adopts the following technical solution:
- a low-chromium corrosion-resistant high-strength polycrystalline superalloy comprising the following elements in percent by weight: from 15 to 18% chromium, from 15% to 20% cobalt, from 0.5% to 1.5% titanium, from 3.5% to 4.5% aluminum, from 5% to 8.5% tungsten, less than or equal to 0.5% silicon, less than or equal to 0.5% manganese, from 0.5% to 1.5% niobium, from 0.03% to 0.08% carbon, and balance being nickel.
- a method for preparing a low-chromium corrosion-resistant high-strength polycrystalline superalloy comprising steps of:
- a further improvement of the present invention lies in that the smelting in step 2) is carried out in a vacuum melting furnace, wherein a vacuum degree in the vacuum melting furnace during smelting is not higher than 1.0 ⁇ 10 -4 MPa.
- a further improvement of the present invention lies in that in step 2), before the temperature reaches 900°C in the course of solidification into the ingot, the cooling rate is controlled not to exceed 15°C/min, and the temperature is cooled to room temperature at a cooling rate exceeding 10°C/min after the temperature reaches 900°C in the course of solidification into the ingot.
- a further improvement of the present invention lies in that in step 2), the time taken from starting solidification of the alloy mother liquor into the ingot till cooling to room temperature does not exceed 15 minutes.
- step 3) specifically comprises: removing the ingot, followed by heating the ingot to a temperature ranging from 1030°C to 1070°C and maintaining the temperature for half an hour, and then continuously heating to a temperature ranging from 1170°C to 1200°C and maintaining the temperature in a heat treatment furnace for a time ranging from 20 to 24 hours, finally cooling to room temperature.
- a further improvement of the present invention lies in that in step 3), a heating rate in the course of heating the ingot to the temperature ranging from 1030°C to 1070°C does not exceed 10°C/min, and the heating rate in the course of heating to the temperature ranging from 1170°C to 1200°C does not exceed 5°C/min.
- a further improvement of the present invention lies in that in step 5), the temperature rises from the room temperature till the temperature ranging from 1110°C to 1130°C at a heating rate not exceeding 10°C/min, and rises from the room temperature till the temperature ranging from 750°C to 770°C at a heating rate not exceeding 10°C/min, followed by rising to the temperature ranging from 840°C to 870°C at a heating rate not exceeding 10°C/min.
- the present invention offers the following beneficial effects:
- the present invention develops a novel superalloy with relatively high Al and Ti contents based on the alloy designing concept of precipitation hardening, wherein the relatively high Al and Cr contents in the alloy also ensure that the alloy has superior anti-oxidation and anti-corrosion properties.
- the alloy prepared according to the method of the present invention has superior strength and corrosion-resistant properties, as well as a good structural stability.
- the alloy matrix is austenitic with an unordered face-centered structure, the average grain size of which is less than 100 ⁇ m; the austenite grain boundary has carbides (NbC and Cr23C6) distributed in a discontinuous pattern, the total volume fraction of the carbides accounting for 5% to 20%; fine spheroidal Ni 3 Al precipitation particles are homogeneously dispersed in the grain, the size of the precipitation particles being not greater than 50nm.
- the tensile yield strengths of the alloy at room temperature and at 850°C are higher than 850MPa and 550MPa, respectively; and after the alloy is exposed to fireside corrosion (N 2 -15% CO 2 -3.5% O 2 -0.1%SO 2 ) at 850°C for 500 hours, the weight change is less than 0.2mg/cm 2 .
- the alloy has a superior structural stability during 850°C thermal exposure.
- a precipitation hardened alloy according to the present invention is a nickel-based superalloy material.
- a low-chromium corrosion-resistant high-strength polycrystalline superalloy comprising the following elements in percent by weight: from 15 to 18% chromium, from 15% to 20% cobalt, from 0.5% to 1.5% titanium, from 3.5% to 4.5% aluminum, from 5% to 8.5% tungsten, less than or equal to 0.5% silicon, less than or equal to 0.5% manganese, from 0.5% to 1.5% niobium, from 0.03% to 0.08% carbon, and balance being nickel.
- a method for preparing a low-chromium corrosion-resistant high-strength polycrystalline superalloy comprising steps of:
- a heat-resisting steel material in this example comprises the following elements in percent by weight: 17% chromium, 20% cobalt, 1.5% titanium, 4.0% aluminum, 7.0% tungsten, 0.5% silicon, 0.5% manganese, 1.0% niobium, 0.04% carbon, balance being nickel.
- a method for preparing the heat-resisting steel material comprises steps of:
- the yield strengths of the alloy prepared according to Example 1 at room temperature and at 850°C are 913MPa and 590MPa, respectively; and the alloy has a weight change of 0.08mg/cm 2 after being exposed to fireside corrosion at 850°C for 500 hours.
- a heat-resisting steel material in this example comprises the following elements in percent by weight: 17% chromium, 20% cobalt, 1.0% titanium, 4.0% aluminum, 8.5% tungsten, 0.5% silicon, 0.5% manganese, 1.5% niobium, 0.04% carbon, balance being nickel.
- a method for preparing the heat-resisting steel material comprises steps of:
- the yield strengths of the alloy prepared according to Example 2 at room temperature and at 850°C are 905MPa and 597MPa, respectively; and the alloy has a weight change of 0.07mg/cm 2 after being exposed to fireside corrosion at 850°C for 500 hours.
- a heat-resisting steel material in this example comprises the following elements in percent by weight: 21% chromium, 20% cobalt, 6.0% aluminum, 7.0 tungsten, 0.5% silicon, 0.5% manganese, 0.04% carbon, balance being nickel.
- a method for preparing the heat-resisting steel material comprises steps of:
- the yield strengths of the alloy prepared according to Comparative Example 1 at room temperature and at 850°C are 692MPa and 352MPa, respectively; and the alloy has a weight change of 0.08mg/cm 2 after being exposed to fireside corrosion at 850°C for 500 hours.
- a heat-resisting steel material in this example comprises the following elements in percent by weight: 21% chromium, 20% cobalt, 2.0% titanium, 4.0% aluminum, 7.0% tungsten, 0.5% silicon, 0.5% manganese, 0.04% carbon, balance being nickel.
- a method for preparing the heat-resisting steel material comprises steps of:
- the yield strengths of the alloy prepared according to Comparative Example 2 at room temperature and at 850°C are 859MPa and567MPa, respectively; and the alloy has a weight change of 1.17mg/cm 2 after being exposed to fireside corrosion at 850°C for 500 hours.
- the alloy prepared according to the present disclosure has a matrix of FCC (Face Centered Cubic) structure, the average grain size being about 30 to 70 ⁇ m, and fine precipitation particles are homogeneously dispersed in the grain.
- the alloy has superior corrosion-resistant and strength properties, with yields at room temperature and at 850°C being no less than 850MPa and 550MPa, respectively. Besides, after being exposed to fireside corrosion at 850°C for 100 hours, the alloy has a weight increase of not more than 0.2mg/cm 2 .
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- Mechanical Engineering (AREA)
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Abstract
Description
- The present invention relates to the field of superalloy materials, and more particularly relate to a low-chromium corrosion-resistant high-strength polycrystalline superalloy and a method of preparing the same.
- Ever-increasing demand in electricity consumption intensifies energy deficiency and environment pollution; therefore, it is pressing to develop an efficient, energy-conservative, and environment-friendly means of power generation. Since fossil-fired power generation has always been a leading power generation technology for a long time in China, it is believed that the most effective means to address the above problems is increase steam parameters of power units. Substantial practices reveal that service performance of the materials for critical components is a primary cause of restricting promotion of boiler unit steam parameters. A superheater/reheater tube, as one of critical components with severest service conditions in a fossil-fired boiler, poses a very stringent requirement on material service performance. The superheater/reheater withstands multiple impacts including high-temperature creep, thermal fatigue, oxidation, and high-temperature fireside corrosion, etc. With substantial increase of main steam parameters of the fossil-fired boiler, it is needed to develop a high-temperature alloy material that may satisfy operating performance requirements of a superheater/reheater tube of a high-parameter power unit in the industry of fossil-fired power generation.
- The superheater/reheater as a component having severest service conditions in a fossil-fired boiler is very demanding on creep rupture strength and corrosion-resistant property of a candidate material. To meet the requirements on material properties of the superheater/ reheater in a high-parameter fossil-fired boiler, a variety of nickel-based wrought superalloy materials have been developed abroad, such as Inconel®740H developed by Special Metals, Haynes®282 developed by Haynes International, CCA 617 developed by Thyssenkrupp, Nimonic 263 developed by Rolls-Royce, FENIX700 developed by Hitachi, TOS1X developed by Toshiba, and LTESR700 developed by Mitsubishi. To ensure a superior creep rupture strength of an alloy, conventional candidate materials generally have a relatively low Al/ Ti ratio. Besides, the relatively high Cr content in the alloy also ensures its anti-oxidation and anti-corrosion properties. However, the ever-increasing steam parameters of fossil-fired generating units pose more harsh challenge to alloy properties. Al (Aluminum) is an important element promoting precipitation hardening in the alloy. A relatively high Al content facilitates increasing Ni3Al volume fraction in the alloy, further conferring a superior strength performance to the alloy. Meanwhile, addition of the Al element also facilitates formation of Al2O3, which substantially promotes high-temperature anti-oxidation and anti-corrosion properties of the alloy. However, addition of the Al element also causes structural instability in the alloy; particularly, a relatively high Al content significantly affects the solidification structure of the alloy.
- An object of the present invention is to provide a low-chromium corrosion-resistant high-strength polycrystalline superalloy and a method of preparing the same, wherein by leveraging the characteristics of Al as an element for strengthening Ni3Al formation in conjunction with its property of improving anti-corrosion property of the alloy, a critical Al content necessary for ensuring formation of Al2O3 in the oxidation/corrosion process of the alloy is added, and a range of Al content in the alloy is stringently controlled while ensuring structural stability of the alloy, so as to promote precipitation of a considerable amount of homogeneously dispersed, second-phase strengthened particles in the alloy to obtain a desired strength property.
- To achieve the object, the present invention adopts the following technical solution:
- A low-chromium corrosion-resistant high-strength polycrystalline superalloy, comprising the following elements in percent by weight: from 15 to 18% chromium, from 15% to 20% cobalt, from 0.5% to 1.5% titanium, from 3.5% to 4.5% aluminum, from 5% to 8.5% tungsten, less than or equal to 0.5% silicon, less than or equal to 0.5% manganese, from 0.5% to 1.5% niobium, from 0.03% to 0.08% carbon, and balance being nickel.
- A method for preparing a low-chromium corrosion-resistant high-strength polycrystalline superalloy, comprising steps of:
- 1) preparing an alloy, wherein the alloy comprises the following elements in percent by weight: from 15% to 18% chromium, from 15% to 20% cobalt, from 0.5% to 1.5% titanium, from 3.5% to 4.5% aluminum, from 5% to 8.5% tungsten, less than or equal to 0.5% silicon, less than or equal to 0.5% manganese, from 0.5% to 1.5% niobium, from 0.03% to 0.08% carbon, and balance being nickel;
- 2) smelting: smelting the prepared alloy into an alloy mother liquor, refining the alloy mother liquor using an electroslag remelting process, followed by cooling, wherein a cooling rate is controlled not to exceed 15°C/min after the alloy mother liquid is solidified into an ingot and before the temperature reaches 900°C in the course of solidifying the alloy mother liquor into the ingot, and cooling at a cooling rate of over 10°C/min to room temperature after the temperature reaches 900°C in the course of solidifying the alloy mother liquor into the ingot;
- 3) homogenizing to obtain a superalloy ingot;
- 4) hot rolling: rolling the superalloy ingot with a total deformation ranging from 50% to 70%, deformation of each pass being controlled within a range from 15% to 25%, and a deformation temperature ranging from 1130°C to 1170°C;
- 5) heat treatment: maintaining the rolled alloy at a temperature ranging from 1110°C to 1130°C for 4 hours, followed by recrystallization; air cooling to room temperature and then maintaining a temperature ranging from 750°C to 770°C for a time ranging from 7 to 9 hours, followed by heating to a temperature ranging from 840°C to 870°C and maintaining the temperature for a time ranging from 1.5 to 2.5 hours, followed by air cooling to room temperature.
- A further improvement of the present invention lies in that the smelting in step 2) is carried out in a vacuum melting furnace, wherein a vacuum degree in the vacuum melting furnace during smelting is not higher than 1.0×10-4 MPa.
- A further improvement of the present invention lies in that in step 2), before the temperature reaches 900°C in the course of solidification into the ingot, the cooling rate is controlled not to exceed 15°C/min, and the temperature is cooled to room temperature at a cooling rate exceeding 10°C/min after the temperature reaches 900°C in the course of solidification into the ingot.
- A further improvement of the present invention lies in that in step 2), the time taken from starting solidification of the alloy mother liquor into the ingot till cooling to room temperature does not exceed 15 minutes.
- A further improvement of the present invention lies in that step 3) specifically comprises: removing the ingot, followed by heating the ingot to a temperature ranging from 1030°C to 1070°C and maintaining the temperature for half an hour, and then continuously heating to a temperature ranging from 1170°C to 1200°C and maintaining the temperature in a heat treatment furnace for a time ranging from 20 to 24 hours, finally cooling to room temperature.
- A further improvement of the present invention lies in that in step 3), a heating rate in the course of heating the ingot to the temperature ranging from 1030°C to 1070°C does not exceed 10°C/min, and the heating rate in the course of heating to the temperature ranging from 1170°C to 1200°C does not exceed 5°C/min.
- A further improvement of the present invention lies in that in step 5), the temperature rises from the room temperature till the temperature ranging from 1110°C to 1130°C at a heating rate not exceeding 10°C/min, and rises from the room temperature till the temperature ranging from 750°C to 770°C at a heating rate not exceeding 10°C/min, followed by rising to the temperature ranging from 840°C to 870°C at a heating rate not exceeding 10°C/min.
- Compared with conventional technologies, the present invention offers the following beneficial effects:
- The present invention develops a novel superalloy with relatively high Al and Ti contents based on the alloy designing concept of precipitation hardening, wherein the relatively high Al and Cr contents in the alloy also ensure that the alloy has superior anti-oxidation and anti-corrosion properties.
- The alloy prepared according to the method of the present invention has superior strength and corrosion-resistant properties, as well as a good structural stability. The alloy matrix is austenitic with an unordered face-centered structure, the average grain size of which is less than 100µm; the austenite grain boundary has carbides (NbC and Cr23C6) distributed in a discontinuous pattern, the total volume fraction of the carbides accounting for 5% to 20%; fine spheroidal Ni3Al precipitation particles are homogeneously dispersed in the grain, the size of the precipitation particles being not greater than 50nm. The tensile yield strengths of the alloy at room temperature and at 850°C are higher than 850MPa and 550MPa, respectively; and after the alloy is exposed to fireside corrosion (N2-15% CO2-3.5% O2-0.1%SO2) at 850°C for 500 hours, the weight change is less than 0.2mg/cm2. Besides, the alloy has a superior structural stability during 850°C thermal exposure.
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Fig. 1 shows a microstructure of an alloy in a heat treated state according to a first example; -
Fig. 2 shows a microstructure of the alloy in a thermal exposure state (850°C /1000h) according to the first example; -
Fig. 3 shows a grain-boundary eutectic structure in a first comparative example; -
Fig. 4 shows a microstructure of the alloy in a thermal exposure state (850°C /1000h) in a second comparative example. - Hereinafter, the present invention will be further illustrated with reference to the following embodiments.
- A precipitation hardened alloy according to the present invention is a nickel-based superalloy material.
- A low-chromium corrosion-resistant high-strength polycrystalline superalloy, comprising the following elements in percent by weight: from 15 to 18% chromium, from 15% to 20% cobalt, from 0.5% to 1.5% titanium, from 3.5% to 4.5% aluminum, from 5% to 8.5% tungsten, less than or equal to 0.5% silicon, less than or equal to 0.5% manganese, from 0.5% to 1.5% niobium, from 0.03% to 0.08% carbon, and balance being nickel.
- A method for preparing a low-chromium corrosion-resistant high-strength polycrystalline superalloy, comprising steps of:
- 1) preparing an alloy, wherein the alloy comprises the following elements in percent by weight: from 15 to 18% chromium, from 15% to 20% cobalt, from 0.5% to 1.5% titanium, from 3.5% to 4.5% aluminum, from 5% to 8.5% tungsten, less than or equal to 0.5% silicon, less than or equal to 0.5% manganese, from 0.5% to 1.5% niobium, from 0.03% to 0.08% carbon, and balance being nickel;
- 2) smelting: smelting the prepared alloy into an alloy mother liquor, refining the alloy mother liquor using an electroslag remelting process, followed by cooling, wherein a cooling rate is controlled not to exceed 15°C/min after the alloy mother liquid is solidified into an ingot and before the ingot temperature reaches 900°C, and the ingot is cooled to room temperature at a cooling rate of over 10°C/min after the ingot temperature reaches 900°C;
- 3) homogenizing, comprising: removing the ingot, followed by heating the ingot to a temperature ranging from 1030°C to 1070°C and maintaining the temperature for half an hour, and then continuously heating to a temperature ranging from 1170°C to 1200°C and maintaining the temperature in a heat treatment furnace for a time ranging from 20 to 24 hours, finally cooling to room temperature to obtain a superalloy ingot;
- 4) hot rolling: rolling the ingot with a total deformation ranging from 50% to 70%, deformation of each pass being controlled within a range from 15% to 25%, and deformation temperature ranging from 1130°C to 1170°C;
- 5) heat treatment: maintaining the rolled alloy at the temperature ranging from 1110°C to 1130°C for 4 hours, followed by recrystallization; air cooling to room temperature and then maintaining a temperature ranging from 750°C to 770°C for a time ranging from 7 to 9 hours, followed by heating to a temperature ranging from 840°C to 870°C and maintaining the temperature for a time ranging from 1.5 to 2.5 hours, followed by air cooling to room temperature.
- A heat-resisting steel material in this example comprises the following elements in percent by weight: 17% chromium, 20% cobalt, 1.5% titanium, 4.0% aluminum, 7.0% tungsten, 0.5% silicon, 0.5% manganese, 1.0% niobium, 0.04% carbon, balance being nickel.
- A method for preparing the heat-resisting steel material comprises steps of:
- 1) preparing raw material: comprising the following elements in percent by weight: 17% chromium, 20% cobalt, 1.5% titanium, 4.0% aluminum, 7.0% tungsten, 0.5% silicon, 0.5% manganese, 1.0% niobium, 0.04% carbon, balance being nickel;
- 2) smelting: placing a ceramic crucible and the prepared raw material simultaneously in a vacuum melting furnace, using a vacuum induction furnace with a vacuum degree not higher than 1.0 ×10-4 Mpa to smelt the prepared alloy into an alloy mother liquor; pre-heating the ceramic crucible using an arc at a low power while the alloy mother liquor is being solidified. After the alloy is completely solidified into an ingot, the ingot is removed to the preheated ceramic crucible, so as to avoid cooling the alloy ingot at a too high cooling rate due to contact between the alloy ingot and the copper crucible.
- 3) homogenizing: removing the ingot, followed by heating the ingot till 1050°C at a rate of 10°C/min and maintaining the temperature for half an hour, and continuously heating to 1200°C at a rate of 5°C/min and maintaining the temperature in a heat treatment furnace for 24 hours, finally cooling to room temperature to obtain a superalloy ingot;
- 4) hot rolling: rolling the ingot with a total deformation ranging from 50% to 70%, deformation of each pass being controlled within a range from 15% to 25%, and the deformation temperature ranging from 1130°C to 1170°C;
- 5) heat treatment: heating the rolled alloy to 1120°C at a rate of 10°C/min and maintaining the temperature for 4 hours, followed by recrystallization; air cooling and maintaining the temperature at 760°C for 8 hours, followed by heating to 860°C and maintaining the temperature for 2 hours; afterwards, air cooling to room temperature.
- The yield strengths of the alloy prepared according to Example 1 at room temperature and at 850°C are 913MPa and 590MPa, respectively; and the alloy has a weight change of 0.08mg/cm2 after being exposed to fireside corrosion at 850°C for 500 hours.
- A heat-resisting steel material in this example comprises the following elements in percent by weight: 17% chromium, 20% cobalt, 1.0% titanium, 4.0% aluminum, 8.5% tungsten, 0.5% silicon, 0.5% manganese, 1.5% niobium, 0.04% carbon, balance being nickel.
- A method for preparing the heat-resisting steel material comprises steps of:
- 1) preparing raw material: comprising the following elements in percent by weight: 17% chromium, 20% cobalt, 1.0% titanium, 4.0% aluminum, 8.5% tungsten, 0.5% silicon, 0.5% manganese, 1.5% niobium, 0.04% carbon, balance being nickel;
- 2) smelting: placing a ceramic crucible and the prepared raw material simultaneously in a vacuum melting furnace, using a vacuum induction furnace with a vacuum degree not higher than 1.0 ×10-4 Mpa to smelt the prepared alloy into an alloy mother liquor; pre-heating the ceramic crucible using an arc at a low power while the alloy mother liquor is being solidified. After the alloy is completely solidified into an ingot, the ingot is removed to the preheated ceramic crucible, so as to avoid cooling the alloy ingot at a too high cooling rate due to contact between the alloy ingot and the copper crucible.
- 3) homogenizing: removing the ingot, followed by heating the ingot till 1050°C at a rate of 10°C/min and maintaining the temperature for half an hour, and continuously heating to 1200°C at a rate of 5°C/min and maintaining the temperature in a heat treatment furnace for 24 hours, finally cooling to room temperature to obtain a superalloy ingot;
- 4) hot rolling: rolling the ingot with a total deformation ranging from 50% to 70%, deformation of each pass being controlled within a range from 15% to 25%, and the deformation temperature ranging from 1130°C to 1170°C;
- 5) heat treatment: heating the rolled alloy to 1120°C at a rate of 10°C/min and maintaining the temperature for 4 hours, followed by recrystallization; air cooling and maintaining the temperature at 760°C for 8 hours, followed by heating to 860°C and maintaining the temperature for 2 hours; afterwards, air cooling to room temperature.
- The yield strengths of the alloy prepared according to Example 2 at room temperature and at 850°C are 905MPa and 597MPa, respectively; and the alloy has a weight change of 0.07mg/cm2 after being exposed to fireside corrosion at 850°C for 500 hours.
- A heat-resisting steel material in this example comprises the following elements in percent by weight: 21% chromium, 20% cobalt, 6.0% aluminum, 7.0 tungsten, 0.5% silicon, 0.5% manganese, 0.04% carbon, balance being nickel.
- A method for preparing the heat-resisting steel material comprises steps of:
- 1) preparing raw material: comprising the following elements in percent by weight: 21% chromium, 20% cobalt, 6.0% aluminum, 7.0% tungsten, 0.5% silicon, 0.5% manganese, 0.04% carbon, balance being nickel;
- 2) smelting: placing a ceramic crucible and the prepared raw material simultaneously in a vacuum melting furnace, using a vacuum induction furnace with a vacuum degree not higher than 1.0 ×10-4 Mpa to smelt the prepared alloy into an alloy mother liquor; pre-heating the ceramic crucible using an arc at a low power while the alloy mother liquor is being solidified. After the alloy is completely solidified into an ingot, the ingot is removed to the preheated ceramic crucible, so as to avoid cooling the alloy ingot at a too high cooling rate due to contact between the alloy ingot and the copper crucible.
- 3) homogenizing: removing the ingot, followed by heating the ingot till 1050°C at a rate of 10°C/min and maintaining the temperature for half an hour, and continuously heating to 1200°C at a rate of 5°C/min and maintaining the temperature in a heat treatment furnace for 24 hours, finally cooling to room temperature to obtain a superalloy ingot;
- 4) hot rolling: rolling the ingot with a total deformation ranging from 50% to 70%, deformation of each pass being controlled within a range from 15% to 25%, and the deformation temperature ranging from 1130°C to 1170°C;
- 5) heat treatment: heating the rolled alloy to 1120°C at a rate of 10°C/min and maintaining the temperature for 4 hours, followed by recrystallization; air cooling and maintaining the temperature at 760°C for 8 hours, followed by heating to 860°C and maintaining the temperature for 2 hours; afterwards, air cooling to room temperature.
- The yield strengths of the alloy prepared according to Comparative Example 1 at room temperature and at 850°C are 692MPa and 352MPa, respectively; and the alloy has a weight change of 0.08mg/cm2 after being exposed to fireside corrosion at 850°C for 500 hours.
- A heat-resisting steel material in this example comprises the following elements in percent by weight: 21% chromium, 20% cobalt, 2.0% titanium, 4.0% aluminum, 7.0% tungsten, 0.5% silicon, 0.5% manganese, 0.04% carbon, balance being nickel.
- A method for preparing the heat-resisting steel material comprises steps of:
- 1) preparing raw material: comprising the following elements in percent by weight: 21% chromium, 20% cobalt, 2.0% titanium, 4.0% aluminum, 7.0% tungsten, 0.5% silicon, 0.5% manganese, 0.04% carbon, balance being nickel;
- 2) smelting: placing a ceramic crucible and the prepared raw material simultaneously in a vacuum melting furnace, using a vacuum induction furnace with a vacuum degree not higher than 1.0 ×10-4 Mpa to smelt the prepared alloy into an alloy mother liquor; pre-heating the ceramic crucible using an arc at a low power while the alloy mother liquor is being solidified. After the alloy is completely solidified into an ingot, the ingot is removed to the preheated ceramic crucible, so as to avoid cooling the alloy ingot at a too high cooling rate due to contact between the alloy ingot and the copper crucible.
- 3) homogenizing: removing the ingot, followed by heating the ingot till 1050°C at a rate of 10°C/min and maintaining the temperature for half an hour, and continuously heating to 1200°C at a rate of 5°C/min and maintaining the temperature in a heat treatment furnace for 24 hours, finally cooling to room temperature to obtain a superalloy ingot;
- 4) hot rolling: rolling the ingot with a total deformation ranging from 50% to 70%, deformation of each pass being controlled within a range from 15% to 25%, and the deformation temperature ranging from 1130°C to 1170°C;
- 5) heat treatment: heating the rolled alloy to 1120°C at a rate of 10°C/min and maintaining the temperature for 4 hours, followed by recrystallization; air cooling and maintaining the temperature at 760°C for 8 hours, followed by heating to 860°C and maintaining the temperature for 2 hours; afterwards, air cooling to room temperature.
- The yield strengths of the alloy prepared according to Comparative Example 2 at room temperature and at 850°C are 859MPa and567MPa, respectively; and the alloy has a weight change of 1.17mg/cm2 after being exposed to fireside corrosion at 850°C for 500 hours.
- Referring to
Figs. 1 ,2 ,3 , and4 , comparisons between the alloys resulting from Example 1 and the comparative examples may reveal that the alloy according to the present invention has a superior structural stability at 850°C without TCP phase precipitated during the high-temperature exposure period. -
- 1) preparing an alloy, wherein the alloy comprises the following elements in percent by weight: 15% chromium, 15% cobalt, 0.5% titanium, 3.5% aluminum, 5% tungsten, less than or equal to 0.5% silicon, less than or equal to 0.5% manganese, 0.5% niobium, 0.03% carbon, and balance being nickel;
- 2) smelting: smelting the prepared alloy into an alloy mother liquor, refining the alloy mother liquor using an electroslag remelting process, followed by cooling, wherein a cooling rate is controlled not to exceed 15°C/min after the alloy mother liquid is solidified into an ingot and before the ingot temperature reaches 900°C, and cooling to room temperature at a cooling rate of over 10°C/min after the ingot temperature reaches 900°C;
- 3) homogenizing: removing the ingot, followed by heating the ingot to 1030°C and maintaining the temperature for half an hour, and then continuously heating to 1170°C and maintaining the temperature in a heat treatment furnace for 23 hours, finally cooling to room temperature to obtain a superalloy ingot.
- 4) hot rolling: rolling the ingot with a total deformation of 50%, deformation of each pass being controlled to 15%, and deformation temperature being 1170°C;
- 5) heat treatment: maintaining the rolled alloy at a temperature of 1110°C for 4 hours, followed by recrystallization; air cooling to room temperature and then maintaining a temperature of 750°C for 9 hours, followed by heating to 840°C and maintaining the temperature for 2.5 hours, followed by air cooling to room temperature.
-
- 1) preparing an alloy, wherein the alloy comprises the following elements in percent by weight: 18% chromium, 17% cobalt, 0.8% titanium, 4.5% aluminum, 6% tungsten, less than or equal to 0.5% silicon, less than or equal to 0.5% manganese, 0.8% niobium, 0.08% carbon, and balance being nickel;
- 2) smelting: smelting the prepared alloy into an alloy mother liquor, refining the alloy mother liquor using an electroslag remelting process, followed by cooling, wherein a cooling rate is controlled not to exceed 15°C/min after the alloy mother liquid is solidified into an ingot and before the ingot temperature reaches 900°C, and cooling to room temperature at a cooling rate of over 10°C/min after the ingot temperature reaches 900°C;
- 3) homogenizing: removing the ingot, followed by heating the ingot to 1070°C and maintaining the temperature for half an hour, and then continuously heating to 1180°C and maintaining the temperature in a heat treatment furnace for 20 hours, finally cooling to room temperature to obtain a superalloy ingot;
- 4) hot rolling: rolling the ingot with a total deformation of 70%, deformation of each pass being controlled to 25%, and deformation temperature being 1130°C;
- 5) heat treatment: maintaining the rolled alloy at a temperature of 1130°C for 4 hours, followed by recrystallization; air cooling to room temperature and then maintaining a temperature of 770°C for 7 hours, followed by heating to 870°C and maintaining the temperature for 1.5 hours, followed by air cooling to room temperature.
- The alloy prepared according to the present disclosure has a matrix of FCC (Face Centered Cubic) structure, the average grain size being about 30 to 70µm, and fine precipitation particles are homogeneously dispersed in the grain. The alloy has superior corrosion-resistant and strength properties, with yields at room temperature and at 850°C being no less than 850MPa and 550MPa, respectively. Besides, after being exposed to fireside corrosion at 850°C for 100 hours, the alloy has a weight increase of not more than 0.2mg/cm2.
Claims (8)
- A low-chromium corrosion-resistant high-strength polycrystalline superalloy, comprising the following elements in percent by weight: from 15 to 18% chromium, from 15% to 20% cobalt, from 0.5% to 1.5% titanium, from 3.5% to 4.5% aluminum, from 5% to 8.5% tungsten, less than or equal to 0.5% silicon, less than or equal to 0.5% manganese, from 0.5% to 1.5% niobium, from 0.03% to 0.08% carbon, and balance being nickel.
- A method for preparing a low-chromium corrosion-resistant high-strength polycrystalline superalloy, comprising steps of:1) preparing an alloy, wherein the alloy comprises the following elements in percent by weight: from 15% to 18% chromium, from 15% to 20% cobalt, from 0.5% to 1.5% titanium, from 3.5% to 4.5% aluminum, from 5% to 8.5% tungsten, less than or equal to 0.5% silicon, less than or equal to 0.5% manganese, from 0.5% to 1.5% niobium, from 0.03% to 0.08% carbon, and balance being nickel;2) smelting: smelting the prepared alloy into an alloy mother liquor, refining the alloy mother liquor using an electroslag remelting process, followed by cooling, wherein a cooling rate is controlled not to exceed 15°C/min after the alloy mother liquid is solidified into an ingot and before the temperature reaches 900°C in the course of solidifying the alloy mother liquor into the ingot, and cooling at a cooling rate of over 10°C/min to room temperature after the temperature reaches 900°C in the course of solidifying the alloy mother liquor into the ingot;3) homogenizing to obtain a superalloy ingot;4) hot rolling: rolling the superalloy ingot with a total deformation ranging from 50% to 70%, deformation of each pass being controlled within a range from 15% to 25%, and a deformation temperature ranging from 1130°C to 1170°C;5) heat treatment: maintaining the rolled alloy at a temperature ranging from 1110°C to 1130°C for 4 hours, followed by recrystallization; air cooling to room temperature and then maintaining a temperature ranging from 750°C to 770°C for a time ranging from 7 to 9 hours, followed by heating to a temperature ranging from 840°C to 870°C and maintaining the temperature for a time ranging from 1.5 to 2.5 hours, followed by air cooling to room temperature.
- The method for preparing a low-chromium corrosion-resistant high-strength polycrystalline superalloy according to claim 2, wherein the smelting in step 2) is carried out in a vacuum melting furnace, wherein a vacuum degree in the vacuum melting furnace during smelting is not higher than 1.0×10-4 MPa.
- The method for preparing a low-chromium corrosion-resistant high-strength polycrystalline superalloy according to claim 2, wherein in step 2), before the temperature reaches 900°C in the course of solidification into the ingot, the cooling rate is controlled not to exceed 15°C/min, and the temperature is cooled to room temperature at a cooling rate exceeding 10°C/min after the temperature reaches 900°C in the course of solidification into the ingot.
- The method for preparing a low-chromium corrosion-resistant high-strength polycrystalline superalloy according to claim 4, wherein in step 2), the time taken from starting solidification of the alloy mother liquor into the ingot till cooling to room temperature does not exceed 15 minutes.
- The method for preparing a low-chromium corrosion-resistant high-strength polycrystalline superalloy according to claim 2, wherein step 3) specifically comprises: removing the ingot, followed by heating the ingot to a temperature ranging from 1030°C to 1070°C and maintaining the temperature for half an hour, and then continuously heating to a temperature ranging from 1170°C to 1200°C and maintaining the temperature in a heat treatment furnace for a time ranging from 20 to 24 hours, finally cooling to room temperature.
- The method for preparing a low-chromium corrosion-resistant high-strength polycrystalline superalloy according to claim 6, wherein in step 3), a heating rate in the course of heating the ingot to the temperature ranging from 1030°C to 1070°C does not exceed 10°C/min, and the heating rate in the course of heating to the temperature ranging from 1170°C to 1200°C does not exceed 5°C/min.
- The method for preparing a low-chromium corrosion-resistant high-strength polycrystalline superalloy according to claim 2, wherein in step 5), the temperature rises from the room temperature till the temperature ranging from 1110°C to 1130°C at a heating rate not exceeding 10°C/min, and rises from the room temperature till the temperature ranging from 750°C to 770°C at a heating rate not exceeding 10°C/min, followed by rising to the temperature ranging from 840°C to 870°C at a heating rate not exceeding 10°C/min.
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| PCT/CN2020/095958 WO2020249113A1 (en) | 2019-06-14 | 2020-06-12 | Low-chromium corrosion-resistant high-strength polycrystalline high-temperature alloy and preparation method therefor |
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| CN111394619A (en) * | 2020-05-08 | 2020-07-10 | 华能国际电力股份有限公司 | High-strength corrosion-resistant nickel-based polycrystalline high-temperature alloy and preparation method thereof |
| CN111411266B (en) * | 2020-05-08 | 2021-03-16 | 中国华能集团有限公司 | A kind of preparation technology of nickel-based high tungsten polycrystalline superalloy |
| CN111394620B (en) * | 2020-05-08 | 2021-01-22 | 华能国际电力股份有限公司 | Machining and forming process of high-strength nickel-based high-temperature alloy bar |
| CN111394621A (en) * | 2020-05-08 | 2020-07-10 | 中国华能集团有限公司 | Deformation high-temperature alloy capable of forming composite corrosion-resistant layer and preparation process thereof |
| CN111471897B (en) * | 2020-05-08 | 2021-06-29 | 华能国际电力股份有限公司 | A kind of high-strength nickel-based superalloy preparation and forming process |
| CN112458339A (en) * | 2020-10-26 | 2021-03-09 | 江苏新核合金科技有限公司 | Corrosion-resistant alloy for high-temperature fan and preparation method thereof |
| CN113667907B (en) * | 2021-08-27 | 2022-05-24 | 华能国际电力股份有限公司 | High-strength corrosion-resistant alloy for 650 ℃ grade thermal power generating unit and preparation method thereof |
| CN115846403B (en) * | 2022-09-23 | 2023-08-15 | 贵州大学 | A cobalt-based alloy with a long rod-like phase structure with a large number of stacking faults and deformation nano-twins and its preparation method |
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| US4769087A (en) * | 1986-06-02 | 1988-09-06 | United Technologies Corporation | Nickel base superalloy articles and method for making |
| US5882586A (en) * | 1994-10-31 | 1999-03-16 | Mitsubishi Steel Mfg. Co., Ltd. | Heat-resistant nickel-based alloy excellent in weldability |
| JP4982324B2 (en) * | 2007-10-19 | 2012-07-25 | 株式会社日立製作所 | Ni-based forged alloy, forged parts for steam turbine plant, boiler tube for steam turbine plant, bolt for steam turbine plant, and steam turbine rotor |
| CN100588730C (en) * | 2008-05-23 | 2010-02-10 | 北京科技大学 | High-chromium-nickel-based superalloy strengthened by chromium-rich precipitates and preparation method thereof |
| JP5165008B2 (en) * | 2010-02-05 | 2013-03-21 | 株式会社日立製作所 | Ni-based forged alloy and components for steam turbine plant using it |
| EP2754529A1 (en) * | 2013-01-11 | 2014-07-16 | Siemens Aktiengesellschaft | Boron-free solder with manganese and germanium, powder and repair method |
| CN110106398B (en) * | 2019-06-14 | 2020-08-18 | 中国华能集团有限公司 | A kind of low-chromium corrosion-resistant high-strength polycrystalline superalloy and preparation method thereof |
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