CN104789817A - ODS (oxide dispersion strengthened) high-temperature alloy material for engine turbine and preparation method of ODS high-temperature alloy material - Google Patents
ODS (oxide dispersion strengthened) high-temperature alloy material for engine turbine and preparation method of ODS high-temperature alloy material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- 229910045601 alloy Inorganic materials 0.000 claims abstract description 37
- 239000002105 nanoparticle Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
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- 229910000601 superalloy Inorganic materials 0.000 claims description 50
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- 238000012545 processing Methods 0.000 claims description 5
- 238000003723 Smelting Methods 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
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- 238000007669 thermal treatment Methods 0.000 claims description 4
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
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Abstract
The invention relates to an ODS (oxide dispersion strengthened) high-temperature alloy material for an engine turbine. The high-temperature alloy material comprises the following components in percentage by weight: 0.22-0.28% of C, 2.1-2.2% of Mn, 0.45-0.61% of Si, 18.3-19.2% of Cr, 8.25-10.4% of Mo, 3.50-3.80% of W, 0.05-0.35% of Al, 0.18-0.27% of Cu, 5.0-9.2% of Fe, 1.0-1.1% of B, 6.7-8.2% of Co, 0.12-0.18% of Zr, 1.12-1.38% of Nb, 1.2-2.8% of composite oxide Y-Ti-O nanoparticles and the balance of Ni and inevitable impurities. The invention further provides a preparation method of the material. A prepared blank has the characteristics of reasonable composition design, reasonable hot-working process, convenience for production organization, strong production operability and strong equipment universality, a produced high-temperature alloy large turbine disk product is high in quality, the structure properties meet standard requirements, the production efficiency is high, and the economic and social benefits are remarkable.
Description
Technical field
The invention belongs to superalloy field, be specially a kind of superalloy and preparation method thereof, be mainly applicable to engine turbine and add ODS high temperature alloy of composite oxides nano particle and preparation method thereof.
Background technology
Superalloy refers to iron, brill, nickel for base, can be on active service and a metalloid material of development more than 600 DEG C under high temperature.Superalloy is single austenitic matrix tissue, have higher hot strength, anti-oxidant and corrosion resistance, there is good structure stability and work reliability, also known as the strong alloy of heat and thermostability superalloy, be often referred to as superalloy (Superalloy) abroad.
Superalloy can have different sorting techniques according to alloying constituent, tissue and moulding process are different.By matrix element classification, mainly contain nickel base superalloy, cobalt-base superalloy and iron-base superalloy, in addition Ling Youyige branch nickel one iron-base superalloy.Divide by preparation technology, wrought superalloy, cast superalloy and powder metallurgy superalloy can be divided into.Can be divided into solid solution strengthened alloy and aging precipitation intensified type alloy by schedule of reinforcement classification, different intensified type alloy has different heat treating regimes.
The motive force of development of superalloy derives from the needs of high-temperature fuel gas turbine, gas turbine engine, and especially aeroengine thrust and efficiency is growing, and improving constantly of engine operating temperature, this just requires that material must possess a higher resistance to warm ability.In the operational process of engine, parts often will be oxidized and various corrosion, therefore, require that the material used will have excellent anti-oxidant and corrosion and heat resistant ability.Along with the progress of the Technologies such as smelting, processing, protection, the research and apply of superalloy has stepped into vigorous growth and application period.Utilize superalloy high-intensity performance, high-temperature wearable and corrosion resistance nature, current superalloy is except except the application of Aeronautics and Astronautics field, also be widely used in the fields such as nuclear power, energy source and power, communications and transportation, petrochemical complex, mine metallurgy, glass building material, paper-making pulping and seawater operation, oneself becomes one of item key of the national metallic substance developmental level of measurement one.
The development of superalloy and the progress of aircraft engine closely related.From the later stage thirties 20th century, the country such as English, moral, U.S. just begins one's study superalloy.The development of aircraft engine advances side by side with superalloy development, inseparable, the former is the major impetus of the latter, and the latter is the former important guarantee.In aircraft engine, temperature is the highest, and the casting turbine blade alloy development of the position that stress is the most complicated especially like this.At the beginning of the forties, the appearance in Britain due to Whittle jet engine at that time, requires than the better sheet material of austenitic stainless steel creep property and bar.Mond company of Britain produces the Nimonic75 alloy adding and lacked C and Ti (Xian Cheng International nickel Co. Ltd. Inco. Ltd.) nineteen forty-one, be used as the blade material used in short-term, added Al afterwards and increased Ti content, soon Nimonic80 alloy has been developed, and the blade material of turbo-jet engine is successfully used as in nineteen forty-two, this be develop the earliest with Ni:(Al, Ti) the turbine blade material strengthened.After this said firm adds B again in the alloy, and adjusts Al, Ti content, succeeds in developing Nimonic80A alloy, for improving creep and enduring quality further, with C.Substitute the part Ni in matrix, developed Nimonic90 alloy, added again Mo and obtain the alloys such as Nimoniel00, form Nimonie system.
China successfully melted out the first stove GH4030 alloy from 1956, eighties of last century have developed GH4037, K406 etc. the sixties in succession.By the development of nearly 60 years, the Study and Development of antioxidant high temperature alloy mainly concentrated on Ni-based or iron-base superalloy at present.Course of its development is in line with international standards, namely defers to the road for development of deforming alloy, casting alloy and oriented monocrystalline alloy, China is become after the U.S. and Russia, English country that the 4th forms independent superalloy system in the world.
As stator blades and the core component being connected blade and turboshaft, reliability and the use properties of the turbine disk are most important, and this is just to the production of the turbine disk, and especially hot-work proposes high requirement.Heavy alloyedly holding warm ability for carrying, adopting the alloy design method reducing Cr, improve refractory element total amount (W, Nb, Ta, Re, Mo etc.) and precipitation phase γ ' content at present.Along with the alloying level of the turbine disk improves constantly, serious segregation makes hot workability worsen, and low cycle fatigue property reduces, and fatigue cracking is easily expanded.
Oxide dispersion intensifying (Oxide Dispersion Strengthened, ODS) superalloy be by tiny oxide particle Dispersed precipitate in matrix alloy, realizing a kind of powder metallurgy superalloy of dispersion-strengthened, is an important development direction of superalloy.Conventional oxide compound is the oxide compound of active metal, as Y
2o
3, ThO
2deng, they have high rigidity and good thermostability and chemical stability, and its strengthening effect can be maintained to close to alloy melting point temperature (0.9Tm), and these ultra-fine oxide compounds are the best disperse phase strengthening matrix under high temperature.
Summary of the invention
Engine turbine is the object of the present invention is to provide to add the ODS high temperature alloy of composite oxides nano particle
and preparation method thereof, there is excellent processability and high hold warm ability, the needs of aircraft engine to turbine disk material can be met.
The complete one of technical scheme of the present invention, each parameter is all through strict control, and quality product is guaranteed.
For reaching this object, the present invention is by the following technical solutions: a kind of engine turbine adds the ODS high temperature alloy of composite oxides nano particle, the composition of described high temperature alloy comprises by weight percentage: C:0.22-0.28%, Mn:2.1-2.2%, Si:0.45-0.61%, Cr:18.3-19.2%, Mo:8.25-10.4%, W:3.50-3.80%, Al:0.05-0.35%, Cu:0.18-0.27%, Fe:5.0-9.2%, B:1.0-1.1%, Co:6.7-8.2%, Zr:0.12-0.18%, Nb:1.12-1.38%, composite oxides Y-Ti-O nano particle: 1.2-2.8%, surplus is Ni and inevitable impurity.
Further, described composite oxides Y-Ti-O nano particle is Y2Ti2O7 and/or Y2TiO5 nano particle, and nano particle size is 10-100nm.
Further, the manufacture method of above-mentioned engine turbine high temperature alloy, comprises the following steps:
(1) raw material prepares: the alloying constituent in the ODS high temperature alloy of interpolation composite oxides nano particle according to claim 1 except composite oxides Y-Ti-O nano particle prepared burden by calculating;
(2) smelting electrode rod, raw material is carried out Melting control vacuum tightness 0.05-0.2Pa, and raw material all melts the constant 35-40 minute of rear maintenance monitor system; Gas clean-up is to 0.001-0.01Pa, and at 1620 DEG C-1640 DEG C refining 10-15 minute, adjusting component makes it meet the requirements, and is then adjusted to 1530-1580 DEG C and pours into consumable electrode rod;
(3) esr: the slag charge proportioning of esr is by weight: CaF2:45-55%, Al2O3:18-23%; CaO:15.5-18%; SiO2:16.5-19.2%, above-mentioned slag charge is heated to molten state, pour in crystallizer, crystallizer and base plate all use water cooling, the consumable electrode of preparation in step 2 rod is slowly dropped in the slag charge of the esr of melting, after the energising starting the arc, adjustment remelting voltage is to 35-65V, electric current 3000-8000A; Consumable electrode rod slowly melts by resistance heat, and the consumable electrode rod drop after fusing reacts through the slag material layer of melting and slag charge and purified, and in the bottom of crystallizer again crystallization, obtains dense structure, even, pure, the ESR ingot of any surface finish;
(4) ESR ingot is made superalloy powder;
(5) superalloy powder that composite oxides Y-Ti-O nano particle and step 4 obtain is carried out ball milling, obtained ODS superalloy powder; Ball milling condition: under argon gas atmosphere protection, with the speed ball milling of per minute 750 ~ 1200 turns, Ball-milling Time 48-120 hour, ball-milling medium: Stainless Steel Ball, ratio of grinding media to material is 5:1 ~ 20:1.
(6) hot isostatic pressing prepares block ODS superalloy, is first loaded in jacket by obtained ODS superalloy powder, carries out soldering and sealing process, arrange vacuum tightness and be less than 10 jacket after vacuumizing
-3pa; Then the jacket that ODS superalloy powder is housed is put into hot isostatic apparatus and carry out hot-pressing processing, obtain block ODS superalloy; Heat and other static pressuring processes condition: temperature is 900 DEG C ~ 1300 DEG C, and pressure is 100 ~ 200MPa, 1 ~ 4 hour treatment time;
(7) thermal treatment: the blank obtained to (6) step carries out solution treatment, by blank heating to 1100-1200 DEG C of insulation 9-12 hour, then air cooling is carried out, and then carry out progressive aging process: first stage ageing treatment: blank is put into heat-treatment heater, isothermal holding is carried out to 900-1000 DEG C by room temperature, soaking time is 12-28h, 720-800 DEG C is cooled to carry out subordinate phase ageing treatment with 30 DEG C/min: at 720-800 DEG C of soaking time 24-36h, 650-700 DEG C is cooled to carry out phase III ageing treatment with 20 DEG C/min: at 650-700 DEG C of insulation 10-12h, finally by blank air cooling to room temperature.
The blank obtained by aforesaid method is more than 820MPa the tensile strength of 1000 DEG C, and yield strength is more than 660MPa, and unit elongation is more than 20%.
Effect of the present invention is:
High temperature alloy of the present invention, has excellent processability and excellent high-temperature behavior, and especially have excellent room temperature to high temperature tensile strength, structure stability is good, and enduring quality and high-performance cast that to forge superalloy TMW suitable.Simultaneously by specific parameter optimization, technique coordinates, and provides reliable preparation method, produces satisfactory product, meanwhile, greatly improve quality product and yield rate, reduces production cost, creates great economic benefit.Follow-up slightly complicated thermal treatment process, makes the quality and performance of foundry goods obtain stronger guarantee.
Embodiment
embodiment 1
A kind of engine turbine high temperature alloy, the composition of described high temperature alloy comprises by weight percentage: C:0.265%, Mn:2.18%, Si:0.54%, Cr:18.7%, Mo:9.3%, W:3.68%, Al:0.28%, Cu:0.21%, Fe:6.5%, B:1.05%, Co:6.81%, Zr:0.16%, Nb:1.21%, Y2Ti2O7 nano particle: 1.35%, surplus is Ni and inevitable impurity, and the manufacture method of described engine turbine high temperature alloy, comprises the following steps:
(1) raw material prepares: the alloying constituent in the ODS high temperature alloy of above-mentioned interpolation composite oxides nano particle except composite oxides Y-Ti-O nano particle prepared burden by calculating;
(2) smelting electrode rod, raw material is carried out Melting control vacuum tightness 0.1Pa, and raw material all melts rear maintenance monitor system constant 37 minutes; Gas clean-up is to 0.008Pa, and 1635 DEG C of refinings 12 minutes, adjusting component made it meet the requirements, and is then adjusted to 1555 DEG C and pours into consumable electrode rod;
(3) esr: the slag charge proportioning of esr is by weight: CaF2:47.1%, Al2O3:20.0%; CaO:16.2%; SiO2:16.7%, is heated to molten state by above-mentioned slag charge, pours in crystallizer, crystallizer and base plate all use water cooling, slowly drop in the slag charge of the esr of melting by the consumable electrode of preparation in step 2 rod, after the energising starting the arc, adjustment remelting voltage is to 40V, electric current 4000A; Consumable electrode rod slowly melts by resistance heat, and the consumable electrode rod drop after fusing reacts through the slag material layer of melting and slag charge and purified, and in the bottom of crystallizer again crystallization, obtains dense structure, even, pure, the ESR ingot of any surface finish;
(4) ESR ingot is made superalloy powder;
(5) superalloy powder that composite oxides Y-Ti-O nano particle and step 4 obtain is carried out ball milling, obtained ODS superalloy powder; Ball milling condition: under argon gas atmosphere protection, with the speed ball milling of per minute 850 turns, Ball-milling Time 90 hours, ball-milling medium: Stainless Steel Ball, ratio of grinding media to material is 10:1;
(6) hot isostatic pressing prepares block ODS superalloy, is first loaded in jacket by obtained ODS superalloy powder, carries out soldering and sealing process, arrange vacuum tightness and be less than 10 jacket after vacuumizing
-3pa; Then the jacket that ODS superalloy powder is housed is put into hot isostatic apparatus and carry out hot-pressing processing, obtain block ODS superalloy; Heat and other static pressuring processes condition: temperature is 1050 DEG C, pressure is 180MPa, 3 hours treatment times;
(7) thermal treatment: the blank obtained to (6) step carries out solution treatment, by blank heating to 1150 DEG C of insulations 11 hours, then air cooling is carried out, and then carry out progressive aging process: first stage ageing treatment: blank is put into heat-treatment heater, isothermal holding is carried out by room temperature to 950 DEG C, soaking time is 15h, 730 DEG C are cooled to carry out subordinate phase ageing treatment with 30 DEG C/min: at 730 DEG C of soaking time 15h, 660 DEG C are cooled to carry out phase III ageing treatment with 20 DEG C/min: at 660 DEG C of insulation 11h, finally by blank air cooling to room temperature.
The blank obtained by aforesaid method is 825MPa the tensile strength of 1000 DEG C, and yield strength is 665MPa, and unit elongation is 22%.
It is reasonable that the present invention has Composition Design, coordinate the feature that rational heat processing technique, organization of production convenience, site operative are strong, equip highly versatile, the superalloy large-scale turbine disk quality product of producing is high, the requirement of structure property conformance with standard, production efficiency is high, economic benefit and social benefit remarkable.
Claims (3)
1. the engine turbine ODS high temperature alloy adding composite oxides nano particle, it is characterized in that: the composition of described high temperature alloy comprises by weight percentage: C:0.22-0.28%, Mn:2.1-2.2%, Si:0.45-0.61%, Cr:18.3-19.2%, Mo:8.25-10.4%, W:3.50-3.80%, Al:0.05-0.35%, Cu:0.18-0.27%, Fe:5.0-9.2%, B:1.0-1.1%, Co:6.7-8.2%, Zr:0.12-0.18%, Nb:1.12-1.38%, composite oxides Y-Ti-O nano particle: 1.2-2.8%, surplus is Ni and inevitable impurity.
2. the engine turbine ODS high temperature alloy adding composite oxides nano particle as claimed in claim 1, it is characterized in that: described composite oxides Y-Ti-O nano particle is Y2Ti2O7 and/or Y2TiO5 nano particle, and nano particle size is 10-100nm.
3. the manufacture method of the engine turbine high temperature alloy according to claim 1-2, is characterized in that, comprise the following steps:
(1) raw material prepares: the alloying constituent in the ODS high temperature alloy of interpolation composite oxides nano particle according to claim 1 except composite oxides Y-Ti-O nano particle prepared burden by calculating;
(2) smelting electrode rod, raw material is carried out Melting control vacuum tightness 0.05-0.2Pa, and raw material all melts the constant 35-40 minute of rear maintenance monitor system; Gas clean-up is to 0.001-0.01Pa, and at 1620 DEG C-1640 DEG C refining 10-15 minute, adjusting component makes it meet the requirements, and is then adjusted to 1530-1580 DEG C and pours into consumable electrode rod;
(3) esr: the slag charge proportioning of esr is by weight: CaF2:45-55%, Al2O3:18-23%; CaO:15.5-18%; SiO2:16.5-19.2%, above-mentioned slag charge is heated to molten state, pour in crystallizer, crystallizer and base plate all use water cooling, the consumable electrode of preparation in step 2 rod is slowly dropped in the slag charge of the esr of melting, after the energising starting the arc, adjustment remelting voltage is to 35-65V, electric current 3000-8000A; Consumable electrode rod slowly melts by resistance heat, and the consumable electrode rod drop after fusing reacts through the slag material layer of melting and slag charge and purified, and in the bottom of crystallizer again crystallization, obtains dense structure, even, pure, the ESR ingot of any surface finish;
(4) ESR ingot is made superalloy powder;
(5) superalloy powder that composite oxides Y-Ti-O nano particle and step 4 obtain is carried out ball milling, obtained ODS superalloy powder; Ball milling condition: under argon gas atmosphere protection, with the speed ball milling of per minute 750 ~ 1200 turns, Ball-milling Time 48-120 hour, ball-milling medium: Stainless Steel Ball, ratio of grinding media to material is 5:1 ~ 20:1;
(6) hot isostatic pressing prepares block ODS superalloy, is first loaded in jacket by obtained ODS superalloy powder, carries out soldering and sealing process, arrange vacuum tightness and be less than 10 jacket after vacuumizing
-3pa; Then the jacket that ODS superalloy powder is housed is put into hot isostatic apparatus and carry out hot-pressing processing, obtain block ODS superalloy; Heat and other static pressuring processes condition: temperature is 900 DEG C ~ 1300 DEG C, and pressure is 100 ~ 200MPa, 1 ~ 4 hour treatment time;
(7) thermal treatment: the blank obtained to (6) step carries out solution treatment, by blank heating to 1100-1200 DEG C of insulation 9-12 hour, then air cooling is carried out, and then carry out progressive aging process: first stage ageing treatment: blank is put into heat-treatment heater, isothermal holding is carried out to 900-1000 DEG C by room temperature, soaking time is 12-28h, 720-800 DEG C is cooled to carry out subordinate phase ageing treatment with 30 DEG C/min: at 720-800 DEG C of soaking time 24-36h, 650-700 DEG C is cooled to carry out phase III ageing treatment with 20 DEG C/min: at 650-700 DEG C of insulation 10-12h, finally by blank air cooling to room temperature.
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| CN106676363A (en) * | 2016-12-14 | 2017-05-17 | 张家港市广大机械锻造有限公司 | Novel high-temperature alloy casting production process |
| CN106755729A (en) * | 2016-12-05 | 2017-05-31 | 东北大学 | A kind of RAFM steel nano reinforcement agent and its preparation and application |
| CN110695360A (en) * | 2019-10-30 | 2020-01-17 | 西安欧中材料科技有限公司 | Method for preparing functionally gradient high-temperature alloy turbine disc |
| CN110983110A (en) * | 2019-12-26 | 2020-04-10 | 南京工程学院 | High-fluidity high-temperature alloy and preparation method thereof |
| CN112250102A (en) * | 2020-10-27 | 2021-01-22 | 航天特种材料及工艺技术研究所 | Y2Ti2O7Composite nano-particles and preparation method and application thereof |
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| CN104789817B (en) | 2016-09-07 |
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