CN1044493C - Nickel-aluminium intermetallic basis alloy - Google Patents

Nickel-aluminium intermetallic basis alloy Download PDF

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CN1044493C
CN1044493C CN95193622A CN95193622A CN1044493C CN 1044493 C CN1044493 C CN 1044493C CN 95193622 A CN95193622 A CN 95193622A CN 95193622 A CN95193622 A CN 95193622A CN 1044493 C CN1044493 C CN 1044493C
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alloy
chromium
atomic percentage
tantalum
nial
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CN1150826A (en
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格哈特·索瑟夫
本尼迪克特·佐莫
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Siemens AG
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Starc Co
Siemens AG
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    • 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
    • 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
    • C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Abstract

A nickel-aluminium intermetallic basis alloy has a structure mainly made of the binary phase NiAl and further contains the elements chromium and tantalum. The total proportion of the elements chromium and tantalum amounts to maximum 12 % by atoms. The preferable content ranges lie from 0.3 to 3.8 % by atoms tantalum and from 1.0 to 9.0 % by atoms chromium. The nickel-aluminium intermetallic basis alloy is characterised in particular by a high oxidation resistance at high temperatures, such as 1350 DEG C. It is therefore suitable for producing pieces exposed to a high and continuous thermal stress, such as gas turbine blades. This high oxidation resistance allows additional anti-oxidation layers to be dispensed with.

Description

Nickel-aluminum intermetallic compound based alloy and application thereof
The present invention relates to a kind of nickel-aluminum intermetallic compound based alloy, it has binary phase NiAl.In addition, the invention still further relates to the application of this nickel-aluminum intermetallic compound based alloy.
A kind of like this nickel-aluminum intermetallic compound based alloy is introduced in paper " NiAl Alloys for HighTemperature Structural Applications " (Journal of Metals, March in 1991, the 44th page was risen) to some extent.
In DE-AS1812144, introduced a kind of high-intensity method made from nickel aluminum of good oxidation.By this method, nickel powder mixes with aluminium powder, then compacting and cooling strain, thus form a kind of molding with energy self-supporting and be mutually related fibrous texture or layered structure.The composition of nickel is at least 80%, and the composition of aluminium is up to 20%.This molding is thermal distortion under each high temperature successively and then.In nickel, except the sosoloid of aluminium, also mainly form compound N i in this case 3Al.This sosoloid and compound N i 3Al can be proved by X-ray analysis.Adopt this method other the compound that between nickel and aluminium, what can produce, from each step of this production method, have no way of learning.
The objective of the invention is to improve the thermomechanical property of alumel, especially its hot strength, scale resistance and thermal-shock resistance.Another object of the present invention is the purposes that provides the alumel after the improvement like this.
The objective of the invention is to realize by a kind of nickel-aluminum intermetallic compound based alloy, it mainly has binary phase NiAl and also has chromium and tantalum in addition, wherein, the atomic percentage conc of chromium and tantalum is counted and can not surpass 12% most, and additional at least a element in alloy selectively from iron, molybdenum, tungsten, niobium and hafnium family, its atom hundred content can reach 1% respectively, but its total content is no more than 3%.The atomic percentage conc of binary phase NiAl is preferably between 70% to 95%, especially between 85% to 90%.The optimum range of the atomic percentage conc of tantalum or chromium is between 0.3% to 3.8% or 1.0% to 9.0%.In such scope, preferably adopt atomic percentage conc at tantalum between 0.3% to 0.9% and atomic percentage conc the chromium between 1.0% to 3%, or atomic percentage conc at tantalum between 1.7% to 3.0% and atomic percentage conc the chromium between 6.0% to 9.0%.
The ratio of tantalum and chromium is preferably 1: 3 or is littler in this case.Adopt such ratio, the concentration of the substitutional element in NiAl reaches maximum value.By adding tantalum and chromium, in nickel-aluminum intermetallic compound based alloy, have thick polynary Laves' phases on the crystal boundary of binary phase NiAl and separate out, wherein composition has element Ni, Al, Cr and Ta.In addition, separate out tiny Laves' phases and α-chromium in NiAl crystal grain inside.In this case, organize best by volume percent be 5% to 11% thick Laves' phases precipitate and the volume percent separated out in NiAl crystal grain inside between 3% to 10% precipitate and remaining NiAl form.Confirmed already particularly advantageously to be that this tissue contained in the volume percent on the crystal boundary and is about 11% Laves' phases precipitate and the volume percent that separates out crystal grain inside in NiAl is about 10% precipitate, that remaining then is NiAl.
If additionally contain at least a element in iron, molybdenum, tungsten and the hafnium family in this alloy, its atomic percentage conc can reach 1.0% respectively, but their total content is no more than 3%, can further make the performance of this alloy obtain certain raising like this.In addition, alloy may have the impurity that tracer element such as oxygen, nitrogen and sulphur and manufacturing cause.
By adding tantalum and chromium, form thick or thin polynary Laves' phases and the α-chromium mentioned by above-mentioned content range.These precipitates can find on the wedge point (Zwickelpunkten) of different NiAl crystal grain usually.If alloying element tantalum or chromium are higher than illustrated amount, may cause with undesirable degree increase amount of separating out.When the volume content of Laves' phases increases too consumingly, form a kind of cellular tissue, wherein Laves' phases plays parent.Laves' phases content is excessive in tissue, dual alloy billet is become fragile and very poor in processability.
Can reach 1% respectively by adding atomic percentage conc, but their total content is no more than one or more elements of 3% iron, molybdenum, tungsten, niobium and hafnium family, the intensity that this alloy bears load at short notice increases, yet its creep strength reduces.By adding hafnium, can improve adhering to of zone of oxidation after the corrosion for the first time.
For reaching the purpose of the relevant use of alloy of the present invention aspect, can adopt this NiAl base alloy to make the parts of internal combustion turbine, especially bear the member of high-temperature load, as the gas turbine blade.When the member of internal combustion turbine, when especially turbine vane is made by this NiAl base alloy, because its high resistance of oxidation, thereby be particularly suitable for life-time service at high temperature, for example, especially under 1350 ℃ temperature environment, use being higher than 1100 ℃.This member is compared with the member that adopts superalloy to make, and its difference is, according to the different not needs one deck additional protection layers of this member of being made by NiAl base alloy that require.Need not to lay the made turbine blade of extra play in the above by a kind of unified alloy composition, can produce very easily, compare, broken away from a bonded difficult problem between each layer with the turbine vane of forming by multilayer.
This intermetallic nickel-aluminum base alloy also is suitable for usually as the such article of material manufacturing,, need have more such article of high strength, high heat resistance, good toughness, good scale resistance and good thermal shock resistance that is.For example, at room temperature, the hot strength at 0.2% yield-point place is higher than 600MPa.At 0.2% yield-point place, the high-temperature capability under 800 ℃ is higher than 200MPa, and is higher than 90MPa in the time of 1000 ℃.Toughness is at least 7MPa/m, and the order of magnitude of oxidation-resistance is 510 -14g 2Cm -4S.
Below by means of describing this nickel-aluminum intermetallic compound based alloy for example in detail.
The alloying constituent of being studied (by atomic percent) is illustrated in the following table 1.Table 1
Ni Al Ta Cr Other
SSM364 45.00 45.00 2.50 7.5
VA2823 44.50 44.50 2.50 8.00 0.39Fe,0.105C
USM2823 44.40 43.90 2.90 8.50 0.14Fe,0.02D
USM2922 45.00 45.00 2.00 8.00
PM75/76 44.10 44.10 2.40 7.70 0.09Fe,0.06C,0.09O,33ppmN,14ppmS
VA892/SP75 44.50 45.20 2.53 7.60 90ppmHf,0.04C,20ppmS,61ppmO
The structure of tissue, that is grain size, the distribution of precipitate and the size of precipitate alter a great deal with production process.Manufacturing route (PM) by thermodynamics processing, extruding (SP) or use powder metallurgy can make being evenly distributed of Laves' phases particulate.
The mechanical property of alloy and the manufacturing processed of manufacturing are closely related.Follow following manufacturing route for this alloy:
-directional freeze as far as possible generates flawless tissue by pouring technology.The process parameter of process parameter and super superalloy corresponding (referring to U.Paul, VDI-progress report Nr.264, VDI press),
-powder metallurgy: by being blown into rare gas element, and and then 1250 ℃ of isobaric compactings of heat down,
-1250 ℃ of down extruding, make homogeneous microstructureization and be adjusted into the crystal grain diameter size of regulation,
-in stressed condition and 1100 ℃ of following hot pressing of multiaxis.
The directional freeze sample has obviously higher intensity, and for example the material of extruding has that reduced or very low intensity.Different alloy and 0.2% yield-point of NiAl in dump test of 2 expressions of tabulating down.
Alloy designations:
SSm364 650 520 451 201 146 94 60 46
VA2823 640 524 414 264 137 83
USM2823 1501 1494 584 404 186 125 88
PM75 814 593 456 284 126 65
PM76 869 562 466 275 113 5l
VA892 133
SP75 730 581 344 294 113 69
The creep strength (MPa) of the alloy that table 3 is illustrated in the compression testing to be studied (with strain rate [1/S] expression 1000 ℃ and 1100 ℃ of creep strengths that following secondary is stable).Table 3
Figure C9519362200071
The creep strength that the creep strength of this alloy is changed metallographic mutually than similar intermetallic is higher, for example is higher than the creep strength of the NiAl or the NiAlCr alloy of binary.
In table 4a, the NiAl alloy and 0.2% yield strength (MPa) of NiAl-Ta-Cr alloy in compression testing of traditional superalloy, binary are contrasted.Table 4a
Temperature: Superalloy Ni 50Al 50 NiAl-Ta-Cr foundry goods/PM75
900℃ 424 47 345/205
1000℃ 135 26 186/126
1100℃ 28 18 125/65
The real alloy of the present invention of last illness that has not attacked the vital organs of the human body is when temperature is higher than 1000 ℃, and its 0.2% yield strength is higher, more superior.
In following table 4b, to superalloy, the NiAl alloy of binary and NiAl-Ta-Cr alloy of the present invention are worked as ε=10 in compression testing -7Creep strength (MPa) stable during 1/S is contrasted.Table 4b
Temperature: Ni 50Al 50 NiAl-Ta-Cr 2823/2922 NiAl-Ta-Cr PM75/SP75
1000℃ 13 79/89 23/19
1100℃ n.b. 33/33 10/6
1200℃ n.b. /21
Abbreviation n.b in the table is that the relevant value of expression is not determined.
Compare with traditional superalloy, the advantage of NiAl-Ta-Cr alloy is that even be higher than 1050 ℃ to 1150 ℃, it still has enough intensity.In this alloy, do not exist because of the loose unexpected decline that causes intensity of solid phase.
In table 5, to the K of the various potteries that check in from existing industrial data ICValue reaches the K of the NiA1-Ta-Cr alloy of producing with powder metallurgy process ICValue is contrasted.Table 5
The NiAl foundry goods NiAl-Ta-Cr foundry goods NiAl-Ta -CrPM NiAl-Ta-Cr SP SiC
K Ic/Mpam 4-5 * 4.5 8 8-11 4.6
* represent that these data take from the Ph D dissertation of the big Reu β of northern Lay mattress-Westfalen-Aachen worker.
The toughness of NiAl base alloy is more far better than the toughness of the NiAl of measured binary and SiC.
It is 510 that this alloy has the order of magnitude -14g 2Cm 4The good oxidation-resistance of S, therefore, it is identical or better with the oxidation-resistance of the NiAl of binary.Compare the layer that at high temperature do not need protection, for example stupalith protective layer with superalloy.Thereby avoided the difficult problem that combines between pottery and metal part branch.
This alloy also has enough thermal shock resistances.In the time of 1350 ℃, this alloy material is not still damaged through 500 temperature cycle.

Claims (12)

1. nickel-aluminum intermetallic compound based alloy, it contains:
The chromium of-atomic percentage conc between 1.0% to 9.0%,
The tantalum of-atomic percentage conc between 0.3% to 3.8%,
Wherein the total content of chromium and tantalum mostly is 12% most,
-and selectively in alloy, adding at least a element from iron, molybdenum, tungsten, niobium and hafnium family, its atomic percentage conc can reach 1.0% respectively, but their total content is no more than 3.0%,
Remaining composition has binary phase NiAl and may cause because of production in-the alloy impurity and tracer element.
2. alloy as claimed in claim 1 is characterized in that, the atomic percentage conc of described binary phase NiAl in tissue amounts between 70% to 95%.
3. alloy as claimed in claim 2 is characterized in that, the atomic percentage conc of described binary phase NiAl in tissue amounts between 85% to 90%.
4. alloy as claimed in claim 1 is characterized in that, it contain atomic percentage conc at tantalum between 0.3% to 3.8% and atomic percentage conc the chromium between 1.0% to 9.0%.
5. alloy as claimed in claim 4 is characterized in that, it contain atomic percentage conc at tantalum between 0.3% to 0.9% and atomic percentage conc the chromium between 1.0% to 3.0%.
6. alloy as claimed in claim 4 is characterized in that, it contain atomic percentage conc at tantalum between 1.7% to 3.0% and atomic percentage conc the chromium between 6.0% to 9.0%.
7. as each described alloy in the claim 1 to 6, it is characterized in that the tantalum that it contains and the ratio of chromium are 1: 3 or littler.
8. as each described alloy in the claim 1 to 6, it is characterized in that, have thick Laves' phases precipitate, and have tiny Laves' phases precipitate and α chromium in some nickel-aluminium grain inside at least at least some NiAl crystal boundaries.
9. alloy as claimed in claim 8, it is characterized in that, its tissue contains the thick Laves' phases precipitate of volumn concentration between 5% to 11%, and tiny Laves' phases precipitate and the α chromium of the volumn concentration of separating out in NiAl crystal grain inside between 3% to 10%.
10. alloy as claimed in claim 9 is characterized in that, it to be organized in that volumn concentration is arranged on the crystal boundary face is 11% Laves' phases precipitate with volumn concentration is arranged in binary NiAl mutually be 10% precipitate.
11. adopt the manufactured materials of the described nickel of above-mentioned each claim-aluminum intermetallic compound based alloy as gas turbine component.
12. member of making by the described alloy of claim 1, it at room temperature has the high strength that is higher than 600MPa at 0.2% yield-point place, the 200MPa of being higher than is arranged at 0.2% yield-point place 800 ℃ the time, the high high-temperature capability that is higher than 90MPa is arranged in the time of 1000 ℃, the excellent toughness (K that is at least 7MP/m is arranged k) and good thermal-shock resistance.
CN95193622A 1994-05-21 1995-05-19 Nickel-aluminium intermetallic basis alloy Expired - Fee Related CN1044493C (en)

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DE4417936A DE4417936C1 (en) 1994-05-21 1994-05-21 Nickel aluminum alloy
DEP4417936.7 1994-05-21

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SE521471C2 (en) 2001-03-27 2003-11-04 Koncentra Holding Ab Piston ring and coating on a piston ring comprising a composite material of a ceramic and an intermetallic compound
CN100422369C (en) * 2006-12-13 2008-10-01 北京航空航天大学 Ti-modified NiAl-Cr(Mo) polyphase eutectic intermetallic compound
BR102013019686B1 (en) 2013-08-01 2020-11-03 Mahle Metal Leve S/A piston ring and its manufacturing process
CN104073688B (en) * 2014-06-19 2016-08-17 湖南科技大学 A kind of NiAl-2.5Ta-7.5Cr alloy is as the application of self-lubricating abrasion-proof material under caustic corrosion operating mode
CN104294328B (en) * 2014-10-23 2017-02-01 上海应用技术学院 Nickel-molybdenum-aluminum-rare earth coating and preparation method thereof
DE102017109156A1 (en) 2016-04-28 2017-11-02 Hochschule Flensburg High-temperature resistant material and its production
CN115595486B (en) * 2022-10-14 2024-03-22 中国科学院金属研究所 Wear-resistant cutting coating for blade tips of high-temperature turbine blades and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0502654A1 (en) * 1991-03-04 1992-09-09 General Electric Company Improved ductility microalloyed NiAL intermetallic compounds

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Publication number Priority date Publication date Assignee Title
DE1812144C3 (en) * 1967-12-06 1974-04-18 Cabot Corp., Boston, Mass. (V.St.A.) Process for the production of a high-strength nickel-aluminum material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0502654A1 (en) * 1991-03-04 1992-09-09 General Electric Company Improved ductility microalloyed NiAL intermetallic compounds

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CN1150826A (en) 1997-05-28
JPH10500453A (en) 1998-01-13
DE4417936C1 (en) 1995-12-07
WO1995032314A1 (en) 1995-11-30
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RU2148671C1 (en) 2000-05-10
CZ342696A3 (en) 1997-08-13

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