AU2003255216B8 - Nickel-base superalloy - Google Patents

Nickel-base superalloy Download PDF

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Publication number
AU2003255216B8
AU2003255216B8 AU2003255216A AU2003255216A AU2003255216B8 AU 2003255216 B8 AU2003255216 B8 AU 2003255216B8 AU 2003255216 A AU2003255216 A AU 2003255216A AU 2003255216 A AU2003255216 A AU 2003255216A AU 2003255216 B8 AU2003255216 B8 AU 2003255216B8
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Australia
Prior art keywords
nickel
ppm
alloy
base superalloy
components
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AU2003255216A
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AU2003255216B2 (en
AU2003255216A1 (en
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Douglas Arrell
Mohamed Nazmy
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Ansaldo Energia IP UK Ltd
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Alstom Technology AG
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Description

BACKGROUND OF THE INVENTION Field of the Invention The invention deals with the field of materials science. It relates to a nickelbase superalloy, in particular for the production of single-crystal components (SX alloy) or components with a directionally solidified microstructure (DS alloy), such as for example blades or vanes for gas turbines. However, the alloy according to the invention can also be used for conventionally cast ;o components.
Discussion of Background Nickel-base superalloys of this type are known. Single-crystal components va made from these alloys have a very good material strength at high temperatures. As a result, by way of example the inlet temperature of gas turbines can be increased, so that the gas turbine becomes more efficient.
Nickel-base superalloys for single-crystal components, as are known from US 4,643,782, EP 0 208 645 and US 5,270,123, for this purpose contain solid-solution-strengthening alloying elements, for example Re, W, Mo, Co, Cr, and y'-phase-forming elements, for example Al, Ta and Ti. The level of high-melting alloying elements Mo, Re) in the basic matrix (austenitic y phase) increases continuously with the increase in the alloy loading temperature. For example, standard nickel-base superalloys for single crystals contain 6-8% of W, up to 6% of Re and up to 2% of Mo (details in by weight). The alloys disclosed in the abovementioned documents have a high creep rupture strength, good LCF (Low Cycle Fatigue) and HCF (High Cycle Fatigue) properties and a high resistance to oxidation.
These known alloys were developed for aircraft turbines and were therefore optimized for short-term and medium-term use, i.e. the loading duration is designed for up to 20,000 hours. By contrast, industrial gas turbine components have to be designed for a loading duration of up to 75,000 hours.
By way of example, after a loading duration of 300 hours, the alloy CMSX-4 described in US 4,643,782, when used in tests in a gas turbine at a temperature of over 10000C, reveals considerable coarsening of the y' phase, which is disadvantageously associated with an increase in the creep rate of the alloy.
It is therefore necessary to improve the oxidation resistance of the known alloys at very high temperatures.
A further problem of the known nickel-base superalloys, for example the alloys which are known from US 5,435,861, consists in the fact that the castability for large components, e.g. gas turbine blades or vanes with a length of more than 80 mm, leaves something to be desired. It is extremely difficult to cast a perfect, relatively large directionally solidified single-crystal component from a nickel-base superalloy, since most of these components have defects, for example small-angle grain boundaries, freckles defects caused by a sequence of uniaxially oriented grains with a high eutectic content), equiaxial scatter boundaries, microporosities, etc. These defects weaken the components at high temperatures, so that the desired service life or operating temperature of the turbine is not reached. However, since a perfectly cast single-crystal component is extremely expensive, industry tends to allow as many defects as possible without the service life or the operating temperature being impaired.
One of the most frequent defects is grain boundaries, which are particularly harmful to the high-temperature properties of the single-crystal article.
Although small-angle grain boundaries have only a relatively small influence on the properties of small components, they are highly relevant with regard to the castability and oxidation characteristics at high temperatures in the case of large SX or DS components.
Grain boundaries are regions of high local disorder of the crystal lattice, since the adjacent grains abut one another in these regions and therefore there is a certain misorientation between the crystal lattices. The greater the misorientation, the greater the disorder, i.e. the larger the number of dislocations in the grain boundaries which are necessary for the two grains to fit together. This disorder is directly related to the performance of the material at high temperatures. It weakens the material when the temperature rises above the equicohesive temperature 0.5 x melting point in K).
This effect is known from GB 2 234 521 A. For example, in a conventional nickel-base single-crystal alloy, the fracture strength drops greatly at a test temperature of 8710C if the misorientation of the grains is greater than This was also recorded with single-crystal components with a directionally solidified microstructure, and consequently opinion has tended to be not to allow misorientations of greater than 6'.
It is also known from the abovementioned GB 2 234521 A that enriching nickel-base superalloys with boron or carbon with directional solidification 4 results in microstructures which have an equiaxial or prismatic grain structure. Carbon Sand boron strengthen the grain boundaries, since C and B cause the precipitation of carbides and borides at the grain boundaries, which are stable at high temperatures.
Moreover, the presence of these elements in and along the grain boundaries reduces the diffusion process, which is a primary cause of grain boundary weakness. It is therefore O possible to increase the misorientations to 100 to 120 yet still achieve good properties of the material at high temperatures. Particularly in the case of large single-crystal t components made from nickel-base superalloys, however, these small-angle grain boundaries have an adverse effect on the properties.
O 10 Any discussion of documents, acts, materials, devices, articles or the like which C has been included in the present specification is solely for the purpose of providing a context for the present invention. It is not to be taken as an admission that any or all of these matters form part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application.
SUMMARY OF THE INVENTION Throughout this specification the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.
Accordingly one aim of the invention is to avoid the abovementioned drawbacks. The invention is based on the aim of developing a nickel-base superalloy which has an improved castability and a higher resistance to oxidation compared to known nickel-base superalloys. Moreover, this alloy is to be particularly suitable, for example, for large gas-turbine single-crystal components with a length of>80 mm.
According to an aspect of the present invention there is provided a nickel-base superalloy characterized by the following chemical composition (details in by weight).
7.7-8.3 Cr 5.0-5.25 Co 2.0-2.1 Mo 7.8-8.3 W 5.8-6.1 Ta 4.9-5.1 Al 1.3-1.4 Ti 0.11-0.15 Si 0.11-0.15 Hf 200-750 ppm C 50-400 ppm B remainder nickel and production-related impurities.
The advantages of the invention consist in the fact that the alloy has very good casting properties and also has an improved resistance to oxidation at high temperatures compared to the previously known prior art.
It is particularly advantageous if the alloy has the following composition: 7.7-8.3 Cr 5.0-5.25 Co 2.0-2.1 Mo 7.8-8.3 W 5.8-6.1 Ta 4.9-5.1 Al 1.3-1.4 Ti 0.11-0.15 Si 0.11-0.15 Hf 200-300 ppm C 50-100 ppm B remainder nickel and production-related impurities. This alloy is eminently suitable for the production of large single-crystal components, for example blades or vanes for gas turbines.
BRIEF DESCRIPTION OF THE DRAWINGS A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, which illustrate an exemplary embodiment of the invention on the basis of quasi-isothermal oxidation diagrams and wherein: Fig. 1 Fig. 2 Fig. 3 Fig. 4 Fig. 5 shows the way in which the specific mass change is dependent on the temperature and time for the comparison alloy CA1; shows the way in which the specific mass change is dependent on the temperature and time for the comparison alloy CA2; shows the way in which the specific mass change is dependent on the temperature and time for the comparison alloy CA3; shows the way in which the specific mass change is dependent on the temperature and time for the comparison alloy CA4, and shows the way in which the specific mass change is dependent on the temperature and time for the alloy according to the invention Al.
DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring now to the drawings, the invention will be explained in more detail with reference to an exemplary embodiment and Figs 1 to Nickel-base superalloys were tested (details in having the chemical composition listed in Table 1 by weight): CA1 CA2 CA3 CA4 Al (CMSX-11B) (CMSX-6) (CMSX-2) (Ren6 Ni Remainder Remainder Remainder Remainder Remainder Cr 12.4 9.7 7.9 7.12 7.7 Co 5.7 5.0 4.6 7.4 5.1 Mo 0.5 3.0 0.6 1.4 W 5.1 8.0 4.9 7.8 Ta 5.18 2.0 6.0 6.5 5.84 Al 3.59 4.81 5.58 6.07 Ti 4.18 4.71 0.99 0.03 1.4 Hf 0.04 0.05 0.17 0.12 C 0.02 B 0.005 Si 0.12 Nb 0.1 Re 2.84 Table 1: Chemical composition of the alloys tested Alloy Al is a nickel-base superalloy for single-crystal components whose composition is covered by the patent claim of the present invention. By contrast, alloys CA1, CA2, CA3 and CA4 are comparison alloys which are part of the known prior art, available under designations CMSX-1 1 B, CMSX-6, CMSX-2 and Ren6 N5. They differ from the alloy according to the invention inter alia above all through the fact that they are not alloyed with C, B and Si.
Carbon and boron strengthen the grain boundaries, in particular including the small-angle grain boundaries which occur in the <001> direction in SX or DS gas turbine blades or vanes made from nickel-base superalloys, since these elements cause the precipitation of carbides and borides at the grain boundaries, which are stable at high temperatures. Moreover, the presence of these elements in and along the grain boundaries reduces the diffusion process, which is a primary cause of the grain boundary weakness. As a result, the castability of long single-crystal components, for example gas turbine blades or vanes with a length of approximately 200 to 230 mm, is considerably improved.
The addition of from 0.11 to 0.15% by weight of Si, in particular in combination with approximately the same order of magnitude of Hf, results in a significant improvement in the resistance to oxidation at high temperatures compared to previously known nickel-base superalloys. This becomes clear from Figs 1 to which each show a quasi-isothermal oxidation diagram for the comparison alloys CA1 to CA4 (Figs 1 to 4) and the alloy according to the invention Al (Fig. The specific mass change Am/A (details in mg/cm 2 at temperatures of 8000C, 9500C, 10500C and 11000C in the range from 0 to 1000 h is illustrated for each of the abovementioned alloys. If the curves are compared, the superiority of the alloy according to the invention is clear, in particular at the high temperatures (10000C) and long aging times.
If nickel-base superalloys with higher C and B contents (max. 750 ppm of C and max. 400 ppm of B) in accordance with claim 1 of the invention are selected, the components produced therefrom can also be cast in the conventional way.
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.

Claims (3)

1. A nickel-base superalloy, characterized by the following chemical composition (details in by weight):
7.7-8.3 Cr 5.0-5.25 Co 2.0-2.1 Mo 7.8-8.3 W 0 5.8-6.1 Ta 4.9-5.1 Al 1.3-1.4 Ti 0.11-0.15 Si 0.11-0.15 Hf
200-750 ppm C 50-400 ppm B remainder nickel and production-related impurities. 2. The nickel-base superalloy as claimed in claim 1, in particular for the 0 production of single-crystal components, characterized by the following chemical composition (details in by weight): 7.7-8.3 Cr 5.0-5.25 Co 2.0-2.1 Mo 7.8-8.3 W 5.8-6.1 Ta 4.9-5.1 Al 1.3-1.4 Ti 0.11-0.15 Si 0 0.11-0.15 Hf 200-300 ppm C 50-100 ppm B remainder nickel and production-related impurities. 3. The nickel-base superalloy as claimed in claim 2, characterized by the following chemical composition (details in by weight): 7.7 Cr 5.1 Co Mo 7.8 W 5.8 Ta Al 1.4 Ti 0.12 Si 0.12 Hf 200 ppm C ppm B remainder nickel and production-related impurities. 4. A nickel-base superalloy substantially as hereinbefore desdribed with reference to the accompanying Figures.
AU2003255216A 2003-10-21 2003-10-21 Nickel-base superalloy Ceased AU2003255216B8 (en)

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AU2003255216A1 AU2003255216A1 (en) 2005-05-05
AU2003255216B2 AU2003255216B2 (en) 2008-04-10
AU2003255216B8 true AU2003255216B8 (en) 2008-05-01

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2105748A (en) * 1981-09-14 1983-03-30 United Technologies Corp Minor element additions to single crystals for improved oxidation resistance
GB2234521A (en) * 1986-03-27 1991-02-06 Gen Electric Nickel-base superalloys for producing single crystal articles having improved tolerance to low angle grain boundaries
US5435861A (en) * 1992-02-05 1995-07-25 Office National D'etudes Et De Recherches Aerospatiales Nickel-based monocrystalline superalloy with improved oxidation resistance and method of production

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2105748A (en) * 1981-09-14 1983-03-30 United Technologies Corp Minor element additions to single crystals for improved oxidation resistance
GB2234521A (en) * 1986-03-27 1991-02-06 Gen Electric Nickel-base superalloys for producing single crystal articles having improved tolerance to low angle grain boundaries
US5435861A (en) * 1992-02-05 1995-07-25 Office National D'etudes Et De Recherches Aerospatiales Nickel-based monocrystalline superalloy with improved oxidation resistance and method of production

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AU2003255216B2 (en) 2008-04-10
AU2003255216A1 (en) 2005-05-05

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