HIGH-TEMPERATURE NICKEL-BASE ALLOY

Information

  • Patent Application
  • 20200172997
  • Publication Number
    20200172997
  • Date Filed
    July 24, 2018
    5 years ago
  • Date Published
    June 04, 2020
    4 years ago
Abstract
A high-temperature nickel-base alloy consists of (in wt. %): C: 0.04-0.1%, S: max. 0.01%, N: max. 0.05%, Cr: 24-28%, Mn: max. 0.3%, Si: max. 0.3%, Mo: 1-6%, Ti: 0.5-3%, Nb: 0.001-0.1%, Cu: max. 0.2%, Fe: 0.1-0.7%, P: max. 0.015%, Al: 0.5-2%, Mg: max. 0.01%, Ca: max. 0.01%, V: 0.01-0.5%, Zr: max. 0.1%, W: 0.2-2%, Co: 17-21%, B: max. 0.01%, O: max. 0.01%, with the rest being Ni, as well as melting-related impurities.
Description

The invention relates to a high-temperature nickel-base alloy.


The material C263 (Nicrofer 5120 CoTi) is used as a material for heat shields in turbochargers or motor-vehicle engines, among other purposes. Within the turbocharger, the heat shield separates the compressor side from the turbine side and is impacted directly by the hot exhaust-gas flow. Since the exhaust-gas temperatures, especially in the internal-combustion engines, are becoming increasingly higher, failure of the structural parts may occur, for example in the form of deformations, which leads to a considerable power loss of the turbocharger.


The exhaust-gas temperatures may be as high as 1050° C., wherein the temperatures occurring at the heat shield range from approximately 900 to 950° C. At these temperatures, the C263 material is no longer creep-resistant. The general composition of the material C263 is given as follows (in wt %): Cr 19.0-21.00, Fe max. 0.7%, C 0.04-0.08%, Mn max. 0.6%, Si max. 0.4%, Cu max. 0.2%, Mo 5.6-6.1%, Co 19.0-21.0%, Al 0.3-0.6%, Ti 1.9-2.4%, P max. 0.015%, S max. 0.007%, B max. 0.005%.


DE 100 52 023 C1 discloses an austenitic nickel-chromium-cobalt-molybdenum-tungsten alloy containing (in mass %) C 0.05-0.10%, Cr 21-23%, Co 10-15%, Mo 10-11%, Al 1.0-1.5%, W 5.1-8.00, Y 0.01-0.1%, B 0.001-0.01%, Ti max. 0.5%, Si max. 0.5%, Fe max. 2%, Mn max. 0.5%, Ni the rest, including unavoidable smelting-related impurities. The material may be used for compressors and turbochargers of internal-combustion engines, structural parts of steam turbines, structural parts of gas-turbine and steam-turbine power plants.


EP 1 466 027 B1 discloses a high-temperature-resistant and corrosion-resistant Ni—Co—Cr-alloy containing (in wt %): Cr 23.5-25.5%, Co 15.0-22.0%, Al 0.2-2.0%, Ti 0.5-2.5%, Nb 0.5-2.5%, up to 2.0% Mo, up to 1.0% Mn, Si 0.3-1.0%, up to 3.0% Fe, up to 0.3% Ta, up to 0.3% W, C 0.005-0.08%, Zr 0.01-0.3%, B 0.001 up to 0.01%, up to 0.05% rare earths as mischmetal, Mg+Ca 0.005-0.025%, optionally up to 0.05% Y, the rest Ni and impurities. In the temperature range between 530 and 820° C., the material can be used as exhaust valves for diesel engines and also as pipes for steam boilers.


In U.S. Pat. No. 6,258,317 B1, an alloy is described that can be used for structural parts of gas turbines at temperatures up to 750° C. and that contains (in wt %): Co 10-24%, Cr 23.5-30%, Mo 2.4-6%, Fe 0-9%, Al 0.2-3.2%, Ti 0.2-2.8%, Nb 0.1-2.5%, Mn 0-2%, up to 0.1% Si, Zr 0.01-0.3%, B 0.001-0.01%, C 0.005-0.3%, W 0-0.8%, Ta 0-1%, the rest Ni and unavoidable impurities.







The task of the invention is to change a material on the basis of C263 with respect to its composition in such a way that the stability of the strength-increasing phase is shifted to higher temperatures. At the same time, attention is to be paid to shifting the stability limits of other phases (e.g. eta phase) to lower temperatures. Furthermore, it is to be endeavored to activate additional hardening mechanisms.


This task is accomplished by a high-temperature nickel-base alloy consisting of (in wt %):


















C
 0.04-0.1%



S
max. 0.01%



N
max. 0.05%



Cr
  24-28%



Mn
max. 0.3%



Si
max. 0.3%



Mo
   1-6%



Ti
 0.5-3%



Nb
0.001-0.1%



Cu
max. 0.2%



Fe
 0.1-0.7%



P
max. 0.015%



Al
 0.5-2%



Mg
max. 0.01%



Ca
max. 0.01%



V
 0.01-0.5%



Zr
max. 0.1%



W
 0.2-2%



Co
  17-21%



B
max. 0.01%



0
max. 0.01%



Ni
the rest as well as smelting-related impurities.










Advantageous further developments of the alloy according to the invention can be inferred from the dependent claims.


The nickel-base alloy according to the invention is intended to be preferably usable for structural parts exposed to structural-part temperatures above 700° C., preferably >900° C., especially >950° C. The objective, namely of shifting the gamma prime phase to higher temperatures, is achieved, wherein simultaneously the stability of other phases may be realized lower than gamma prime and likewise at lower temperatures.


In the following, important cases of application of the alloy are addressed:


Automotive





    • Exhaust-gas systems

    • Turbochargers

    • Sensors

    • Valves

    • Pipes

    • High-temperature filters or parts thereof

    • Seals

    • Spring elements


      Flying or stationary turbines

    • Blades

    • Guide vanes

    • Sensors

    • Pipes

    • Cones

    • Housings


      Power plants

    • Pipes

    • Sensors

    • Valves

    • Forgings

    • Turbines

    • Turbine housings





The said structural parts are used together and separately in hot and highly stressed atmospheres, wherein continuous structural-part temperatures, sometimes above 900° C., are encountered. Beyond that, oxygen-containing atmospheres are encountered, for example in passenger-car or heavy-truck engines, jet engines or gas turbines.


The alloy according to the invention has a high high-temperature strength and creep strength, wherein simultaneously a high thermal corrosion resistance (e.g. to exhaust gases) is also achieved.


Beyond this, the alloy according to the invention is fatigue-resistant at high temperatures, especially above 900° C.


Possible product forms are:

    • Strip
    • Sheet
    • Wire
    • Bars
    • Forgings
    • Powders for additive manufacturing (e.g. 3D printing) and traditional powders (e.g. sintering)
    • Pipes (welded or seamless)


The following elements may be varied (in wt %) as indicated in the following, for optimization of the desire parameters:


















Cr
  24-26%



Mo
  2-6%, especially 4-6%



Mo
 1.5-2.5%



Ti
 0.5-2.5%, especially 1.5-2.5%



Al
 0.5-1.5%



V
0.01-0.2%



W
 0.2-1.5%, especially 0.5-1.5%



Co
18.5-21%










It is of advantage when the sum of Ti+Al (in wt %) is at least 1%. In certain cases of use, it may be expedient when the sum of Ti+Al (in wt %) is at least 1.5%, especially at least 2%.


According to a further idea of the invention, the Ti/Al ratio should be at most 3.5, especially at most 2.0%.


By reduction of the Ti/Al ratio, no or only little eta-phase Ni3Ti is able to form.


The high-temperature nickel-base alloy according to the invention is preferably usable for industrial-scale production (>1 metric ton).


The advantages of the alloy according to the invention will be explained in more detail on the basis of examples:


In Table 1, the prior art (Nicrofer 5120 CoTi—produced on the industrial scale) is compared with an identical reference batch (laboratory) as well as with several alloy compositions according to the invention.


In Table 2, the prior art (Nicrofer 5120 CoTi—produced on the industrial scale) is compared with several batches produced on the industrial scale.












TABLE 1








Nicrofer 5120





CoTi Batch
250573
250574



413297,
New Design
New Design



produced on
work 0
work 1













industrial scale
Target
Actual
Target
Actual





C
0.049
0.055
0.051
0.055
0.061


S
0.002
0.002
0.0027
0.002
0.0027


N
0.004
0.004
0.005
0.004
0.006


Cr
19.99
25.00
24.46
25.00
25.00


Ni the
51.3313
the
46.6903
the
51.5683


rest

rest

rest



Mn
0.07
0.07
0.01
0.07
0.01


Si
0.04
0.04
0.02
0.04
0.05


Mo
5.85
5.85
5.79
3.00
2.73


Ti
2.09
1.60
1.56
1.20
1.16


Nb
0.01
0.01
0.01
0.01
0.02


Cu
0.01
0.01
0.01
0.01
0.01


Fe
0.23
0.23
0.25
0.23
0.23


P
0.002
0.002
0.002
0.002
0.002


Al
0.46
0.53
0.51
0.70
0.65


Mg
0.001
0.001
0.001
0.001
0.002


Pb
0.0002






Sn
0.001






Ca
0.01






V
0.01
0.05
0.01
0.05
0.05


Zr
0.01
0.01
0.01
0.01
0.01


W
0.01
0.50
0.47
0.50
0.50


Co
19.81
20.00
20.13
18.00
17.93


B
0.003
0.003
0.003
0.003
0.003


As
0.001






Rare
0.0003






earths







Te
0.0001






Bi
0.






Ag
0.0001






0
0.005
0.005
0.005
0.005
0.005


Ti + Al
2.55
2.13
2.07
1.90
1.81


Ti/Al
4.5435
3.0189
3.0588
1.7143
1.7846















Nicrofer 5120






CoTi Batch
250575
250576
250577



413297,
New Design
New Design
New Design



produced on
work 2
work 3
work 4















industrial scale
Target
Actual
Target
Actual
Target
Actual





C
0.049
0.055
0.058
0.055
0.056
0.055
0.056


S
0.002
0.002
0.002
0.002
0.002
0.002
0.003


N
0.004
0.004
0.005
0.004
0.006
0.004
0.004


Cr
19.99
25.00
24.57
25.00
24.52
25.00
24.83


Ni the
51.3313
the
51.796
the
51.885
the
46.298


rest

rest

rest

rest



Mn
0.07
0.07
0.01
0.07
0.01
0.07
0.01


Si
0.04
0.04
0.02
0.04
0.04
0.04
0.03


Mo
5.85
2.008
1.96
2.00
1.92
5.85
5.58


Ti
2.09
1.68
1.62
1.78
1.77
1.60
1.69


Nb
0.01
0.01
0.01
0.01
0.01
0.01
0.02


Cu
0.01
0.01
0.01
0.01
0.01
0.01
0.01


Fe
0.23
0.23
0.23
0.23
0.24
0.23
0.23


P
0.002
0.002
0.002
0.002
0.002
0.002
0.002


Al
0.46
0.95
0.96
1.00
0.98
0.95
1.04


Mg
0.001
0.001
0.001
0.001
0.001
0.001
0.001


Pb
0.0002








Sn
0.001








Ca
0.01








V
0.01
0.05
0.08
0.05
0.08
0.05
0.04


Zr
0.01
0.01
0.01
0.01
0.01
0.01
0.01


W
0.01
1.00
0.92
1.00
0.94
0.50
0.54


Co
19.81
18.00
17.73
18.00
17.51
20.00
19.60


B
0.003
0.003
0.003
0.003
0.003
0.003
0.002


As
0.001








Rare
0.0003








earths









Te
0.0001








Bi
0.








Ag
0.0001








O
0.005
0.005
0.003
0.005
0.005
0.005
0.004


Ti + Al
2.55
2.63
2.58
2.78
2.75
2.55
2.73


Ti/Al
4.5435
1.7684
1.6875
1.78
1.8061
1.6842
1.625










Table 1 (continued)











TABLE 2








Nicrofer 5120
Analysis of hot strip













CoTi Batch
Batch
Batch
Batch
Batch



413297,
335449
334549
334547
334547



produced on
Analysis
Analysis
Analysis
Analysis



industrial scale
of top 5200
of bottom 5200
of top 5100
of bottom 5100















C
0.049
0.051
0.05
0.051
0.051


S
0.002
0.002
0.002
0.002
0.002


N
0.004
0.008
0.009
0.008
0.01


Cr
19.99
24.9
24.9
24.9
24.9


Ni the
51.3313
45.11
45.07
45.12
45.09


rest







Mn
0.07
0.01
0.01
0.01
0.01


Si
0.04
0.06
0.07
0.06
0.05


Mo
5.85
5.82
5.83
5.81
5.83


Ti
2.09
1.69
1.69
1.69
1.69


Nb
0.01
0.02
0.02
0.02
0.02


Cu
0.01
0.01
0.01
0.01
0.01


Fe
0.23
0.53
0.53
0.53
0.53


P
0.002
0.002
0.002
0.002
0.002


Al
0.46
1.08
1.08
1.08
1.08


Mg
0.001
0.003
0.003
0.003
0.003


Pb
0.0002
0.0002
0.0002
0.0002
0.0002


Sn
0.001
0.01
0.01
0.01
0.01


Ca
0.01
0.01
0.01
0.01
0.01


V
0.01
0.07
0.07
0.07
0.07


Zr
0.01
0.02
0.01
0.02
0.02


W
0.01
0.58
0.59
0.59
0.58


Co
19.81
20.01
20.03
20.00
20.03


B
0.003
0.004
0.004
0.004
0.004


As
0.001
0.001
0.001
0.001
0.001


Rare
0.0003






earths







Te
0.0001






Bi
0.
0.00003
0.00003
0.00003
0.00003


Ag
0.0001






O
0.005






Ti + Al
2.55
2.77
2.77
2.77
2.77


Ti/Al
4.5435
1.565
1.565
1.565
1.565









Respectively 8 kg per heat of starting materials were used (Table 1). After casting, spectral analyses of the samples were performed. The samples were then rolled to a thickness of 6 mm. By further rolling (with intermediate annealing) on a laboratory roll, the samples were rolled to a final thickness of 0.4 mm.


The solution annealing was carried out at 1150° C. for 30 minutes and followed by quenching in water.


A precipitation hardening was carried out at temperatures of 800, 850, 900 or 950° C. for 4/ 8/16 hours followed by quenching in water.


In the process, the variants 250575 to 250577 exhibited a very high hardness level compared with the prior art, as did respectively the variants 250573 and 250574. This means that the hardness-increasing phase (here gamma prime) is still stable.


For industrial-scale applications (Table 2), the material is produced in a medium-frequency induction furnace then cast as a continuous casting in slab form. Then the slabs are remelted in the electroslag remelting furnace to further slabs (or respectively bars). Thereafter the respective slab is hot rolled, for production of strip material in thicknesses of approximately 6 mm. This is followed by a process of cold-rolling of the strip material to a final thickness of approximately 0.4 mm.


In this way a starting material for deep-drawn or stamped products is now obtained. If necessary, a thermal process may still be applied, depending on the product.


For production of structural parts for aeronautics, the following manufacturing process is conceivable:


VIM-VAR

The product form after the VAR may be a slab or a bar.


The forming may be carried out by rolling or forging.


For production of structural parts for power plants or motor vehicles, the following manufacturing process is also conceivable:


VIM-ESR

Here also, forming by forging or rolling is conceivable.



FIG. 1 shows the creep elongation of various materials in dependence on the time for a typical application temperature of 900° C. as well as a load of 60 MPa. Results are illustrated for the materials C-263 Standard (Nicrofer 5120 CoTi), C-264 variant 76 (batch 250576) and C-264 variant 77 (batch 250577).


In the case of the standard version, it is apparent that, at given temperature and load, the material fails after less than 100 hours.


The other two variants both exhibit endurance times of approximately 400 hours and respectively 550 hours.


Variants 76 and 77 exhibit improved endurance times, which in the operating condition lead to a greater creep resistance and thus to much smaller structural-part deformation.

Claims
  • 1. A high-temperature nickel-base alloy comprising (in wt %):
  • 2. A nickel-base alloy according to claim 1, containing (in wt %) Cr 24-26%.
  • 3. The nickel-base alloy according to claim 1, containing (in wt %) Mo 2-6%.
  • 4. The nickel-base alloy according to claim 1, containing (in wt %) Mo 1.5-2.5%.
  • 5. The nickel-base alloy according to claim 1, containing (in wt %) Mo 4-6%.
  • 6. The nickel-base alloy according to claim 1, containing (in wt %) Ti 0.5-2.5%.
  • 7. The nickel-base alloy according to claim 1, containing (in wt %) Ti 1.5-2.5%.
  • 8. The nickel-base alloy according to claim 1, containing (in wt %) Al 0.5-1.5%.
  • 9. The nickel-base alloy according to claim 1, containing (in wt %) V 0.01-0.2%.
  • 10. The nickel-base alloy according to claim 1, containing (in wt %) W 0.5-1.5%.
  • 11. The nickel-base alloy according to claim 1, wherein the sum of Ti+Al (in wt %) is at least 1%.
  • 12. The nickel-base alloy according to claim 1, wherein the sum of Ti+Al (in wt %) is at least 1.5%, especially at least 2%.
  • 13. The nickel-base alloy according to claim 1, wherein the Ti/AI ratio is at most 3.5%, especially at most 2.0%.
  • 14. The nickel-base alloy according to claim 1, usable for structural parts exposed to structural-part temperatures >700° C., especially >900° C. or respectively >950° C.
  • 15. The nickel-base alloy according to claim 1, usable for structural parts in internal-combustion engines.
  • 16. The nickel-base alloy according to claim 1, usable as structural parts of turbochargers.
  • 17. The nickel-base alloy according to claim 1, usable for structural parts in flying or stationary turbines, especially gas turbines.
  • 18. The nickel-base alloy according to claim 17, usable for blades or guide elements in flying or stationary turbines, especially gas turbines.
  • 19. The nickel-base alloy according to claim 1, usable for structural parts in power plants.
  • 20. The nickel-base alloy according to claim 19, usable for pipes or sensors in power plants.
Priority Claims (1)
Number Date Country Kind
10 2017 007 106.3 Jul 2017 DE national
PCT Information
Filing Document Filing Date Country Kind
PCT/DE2018/100663 7/24/2018 WO 00