US20130206287A1
2013-08-15
13/816,905
2011-08-15
A Co-based alloy containing not less than 0.001 mass % and less than 0.100 mass % of C, not less than 9.0 mass % and less than 20.0 mass % of Cr, not less than 2.0 mass % and less than 5.0 mass % of Al, not less than 13.0 mass % and less than 20.0 mass % of W, and not less than 39.0 mass % and less than 55.0 mass % of Ni, with the remainder being made up by Co and unavoidable impurities, wherein the contents of Mo, Nb, Ti and Ta which are included in the unavoidable impurities are as follows: Mo<0.010 mass %, Nb<0.010 mass %, Ti<0.010 mass %, and Ta<0.010 mass %.
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C22C19/056 » CPC further
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%
C22C19/057 » CPC further
Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
C22F1/10 » CPC main
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
C22C30/00 » CPC further
Alloys containing less than 50% by weight of each constituent
C22C19/05 IPC
Alloys based on nickel or cobalt based on nickel with chromium
The present invention relates to a Co-based alloy suitable for various components required to have a high strength in a high-temperature environment, such as for a gas turbine, an aircraft engine, a chemical plant, a vehicle engine and a high-temperature furnace. In particular, it relates to a Co-based suitable for casting.
A Ni-based alloy, a Co-based alloy, an Fe-based alloy or the like have been known as a superalloy used at a high-temperature. The Ni-based alloy is precipitation-strengthened by a Ξ³β² phase having an L12 structure (Ni3(Al, Ti)), and exhibits a reverse temperature dependency where strength increases as a temperature increases. In addition, the Ni-based alloy has excellent high-temperature properties such as heat resistance, corrosion resistance, oxidation resistance and creep resistance. Thus, the Ni-based alloy is used for various purposes which require a high strength in a high-temperature environment. However, there is a problem that the Ni-based alloy is inferior in machinability and hot workability.
In contrast, the Co-based alloy is used rather than the Ni-based alloy for high-temperature applications when particularly corrosion resistance and ductility are required. However, there was a problem that a conventional Co-based alloy has a lower high-temperature strength than the Ni-based alloy and is inferior in hot workability to the Ni-based alloy, since a Ξ³β²-type intermetallic compound effective for improving the high-temperature strength properties of the Co-based alloy was not known.
In order to solve the problem, various attempts have been conventionally proposed.
For example, WO 2007/032293 A1 discloses a Co-based alloy including, by mass, 0.1 to 10% of Al, 3.0 to 45% of W, and the balance of Co and inevitable impurities, and having a precipitate of an L12-type intermetallic compound Co3(Al, W).
WO 2007/032293 A1 discloses that a high-temperature strength is increased by uniformly and finely precipitating Co3(Al, W) in a matrix and that hot working becomes possible by adjusting the Co-based alloy to have a predetermined composition.
JP-A-2009-228024 discloses a Co-based alloy including not less than 0.1 and not more than 20.0 mass % of Cr, not less than 1.0 and not more than 6.0 mass % of Al, not less than 3.0 and not more than 26.0 mass % of W, not more than 50.0 mass % of Ni, and the balance of Co and inevitable impurities, and satisfying that Cr+Al is not less than 5.0 and not more than 20.0 mass %, and that a volume ratio of second phases composed of a ΞΌ phase represented by A7B6 and a Laves phase represented by A2B is not more than 10%.
JP-A-2009-228024 discloses that the Co-based alloy exhibits high-temperature strength equal to or greater than that of a Ni-based alloy, when the alloy includes predetermined amounts of Al and W and is subjected to homogenizing heat treatment and aging treatment under predetermined conditions to precipitate a Co3(Al, W) strengthening phase.
The Co-based alloy including precipitated Co3(Al, W) as the strengthening phase (Ξ³β² phase) exhibits high-temperature strength properties equal to or greater than those of a Ni-based alloy. However, the Co-based alloy including Al and W may have a second phase precipitate depending on heat treatment conditions, that is harmful to processing. Thus, hot workability may be significantly decreased. In particular, hot workability is an important property for an alloy for casting, and thus a balance between hot workability and strength is necessary.
As disclosed in JP-A-2009-228024, precipitation of the second phase can be suppressed to some extent and hot workability can be improved by optimizing the composition of the alloy. However, high-temperature strength properties of a conventional alloy are not always sufficient.
It is an object of the invention to provide a Co-based alloy having a high-temperature strength higher than that of a conventional Co-based alloy and hot workability equal to or greater than that of the conventional alloy, and being suitable for casting.
In order to solve the problem, a Co-based alloy according to the invention comprises
not less than 0.001 and less than 0.100 mass % of C,
not less than 9.0 and less than 20.0 mass % of Cr,
not less than 2.0 and less than 5.0 mass % of Al,
not less than 13.0 and less than 20.0 mass % of W,
not less than 39.0 and less than 55.0 mass % of Ni, and
the balance being Co and inevitable impurities. Mo, Nb, Ti and Ta in the impurities are as follows:
less than 0.010 mass % of Mo,
less than 0.010 mass % of Nb,
less than 0.010 mass % of Ti, and
less than 0.010 mass % of Ta.
A Co-based alloy including Al and W easily generates a phase harmful to hot workability. In particular, when excessive W is contained, a harmful phase is generated within grains and in grain boundaries, and thus hot workability is significantly decreased.
However, when a Co-based alloy has a composition adjusted in a predetermined range (in particular Al and W contents) and is subjected to homogenizing heat treatment, the Co-based alloy can include less harmful phase. In addition, when the alloy is subjected to solution heat treatment and aging treatment under predetermined conditions after hot working, a Co3(Al, W) strengthening phase (Ξ³β² phase) is precipitated. Furthermore, when a predetermined amount of carbon is added to the Co-based alloy containing predetermined amounts of Al, W and Cr, carbide containing W and/or Cr is precipitated in addition to the Ξ³β² phase after the aging treatment. At this time, granular carbide can be precipitated in grain boundaries of a Ξ³ phase matrix by optimizing the carbon content. The granular carbide precipitated in the grain boundaries has a large effect of suppressing grain boundary sliding at a high temperature.
That is, a predetermined amount of carbide is precipitated in the grain boundaries in addition to the precipitation of the Ξ³β² phase, thereby a creep rupture property or high-temperature ductility, which is specifically required for a high-temperature material, is remarkably improved in comparison to a conventional Co-based alloy. Accordingly, a Co-based alloy having endurance strength equal to or greater than that of an existing Ni-based alloy can be obtained.
Other purposes, features and advantages of the invention will become apparent from the following description of Embodiments of the invention with reference to attached drawings.
FIG. 1 is a photograph of a microstructure of a ruptured portion in a Co-based alloy (Example 1) before a creep rupture test.
FIG. 2 is a photograph of a microstructure of the ruptured portion in the Co-based alloy (Example 1) after the creep rupture test.
Hereinafter, an embodiment of the invention will be described in detail.
A Co-based alloy according to the invention includes following elements, and the balance is Co and inevitable impurities. The elements, addition ranges thereof, and reasons for determining the ranges are explained as follows.
(1) Not Less than 0.001 and Less than 0.100 Mass % of Carbon
Carbon bonds to W and Cr, and contributes to carbide generation within grains and in grain boundaries. Precipitation of granular carbide in the grain boundaries is effective mainly for grain boundary strengthening, and improves hot workability and high-temperature strength. In particular, since elongation and reduction at a high temperature are improved due to improvement of the grain boundary strength, the granular carbide precipitation has a large effect of improving a tensile and creep rupture properties. In order to obtain the effects, the carbon content needs to be not less than 0.001 mass %. More preferably, the carbon content is not less than 0.005 mass %.
However, when carbon is added excessively, strength properties are decreased since grain strength is increased due to acceleration of carbide generation within the grains and precipitation of film carbide in the grain boundaries. Therefore, the carbon content needs to be less than 0.100 mass %. More preferably, the carbon content is less than 0.050 mass %.
In the Co-based alloy according to the invention, carbide is precipitated in the grain boundaries in an optimum form by optimizing the carbon content in addition to the contents of Cr and W, thereby improving high-temperature ductility, and thus significant improvement of properties can be achieved. The term βcarbideβ means various kinds of carbides mainly containing carbon and Cr and/or W.
(2) Not Less than 9.0 and Less than 20.0 Mass % of Cr
Cr is effective for improving oxidation resistance since Cr bonds to oxygen and forms a dense Cr2O3 layer on its surface. If a Cr content is low, it becomes difficult to form the dense Cr2O3 layer, and sufficient oxidation resistance can not be obtained. In addition, Cr bonds to carbon and generates various kinds of carbides within grains and in grain boundaries, and thus, contributes to improvement of hot workability and high-temperature ductility. In order to obtain the effects, the Cr content needs to be not less than 9.0 mass %. Cr is added, more preferably, not less than 10.0 mass %, and further preferably, not less than 10.5 mass %.
However, when the Cr content becomes excessive, a melting point of the Co-based ally is lowered to cause a decrease in mechanical properties at a high temperature. Therefore, the Cr content needs to be less than 20.0 mass %. The Cr content is, more preferably, less than 19.5 mass %, and further preferably, less than 18.5 mass %.
In the Co-based alloy according to the invention, carbide is precipitated in an optimum form by optimizing the Cr content, and thus, significant improvement of high-temperature ductility can be achieved.
(3) Not Less than 2.0 and Less than 5.0 Mass % of Al
Al stabilizes an L12-type intermetallic compound phase (Ξ³β² phase) of Co3(Al, W). Al is a necessary element for precipitating the metastable Ξ³β² phase as a stable phase and improves high-temperature strength. If an Al content is low, a sufficient amount of the Ξ³β² phase for improving strength properties can not be generated. In addition, similar to Cr, Al improves oxidation resistance since it generates Al2O3. In order to obtain the effects, the Al content needs to be not less than 2.0 mass %. The Al content is, more preferably, not less than 2.5 mass %, and further preferably, not less than 3.0 mass %.
However, when the Al content becomes excessive, a melting point of the Co-based alloy is raised and high-temperature properties (hot workability and high-temperature ductility) are decreased. Therefore, the Al content needs to be less than 5.0 mass %. The Al content is, more preferably, less than 4.5 mass %, and further preferably, less than 4.3 mass %.
The βL12-type intermetallic compound phase (Ξ³β² phase) of Co3(Al, W)β includes not only the Ξ³β². phase made of Co, Al and W, but also that in which a part of a Co and/or an (Al, W) site is replaced by other element(s).
(4) Not Less than 13.0 and Less than 20.0 Mass % of Tungsten
Tungsten stabilizes the L12-type intermetallic compound phase (Ξ³β² phase) of Co3(Al, W). Tungsten is a necessary element for generating the Ξ³β² phase that is effective for obtaining a high-temperature strength. If the tungsten content is low, an amount of the Ξ³β² phase sufficient for improving strength can not be generated. In addition, tungsten bonds to carbon and generates various carbides. Precipitation of the carbides in grain boundaries is effective for improving high-temperature strength, specifically high-temperature ductility (elongation, reduction). In order to obtain the effects, the tungsten content needs to be not less than 13.0 mass %. The tungsten content is, more preferably, not less than 14.5 mass %, and further preferably, not less than 15.0 mass %.
However, when the tungsten content becomes excessive, a harmful phase, such as ΞΌ phase represented by A7B6, is formed within grains and in grain boundaries and thus hot workability is significantly decreased. Therefore, the tungsten content needs to be less than 20.0 mass %. The tungsten content is, more preferably, less than 19.0 mass %, and further preferably, less than 18.0 mass %.
The βA7B6 compound (ΞΌ phase)β is a compound derived from Co7W6, and also includes a compound in which an A site (Co site) is replaced by Ni, Cr, Al, Fe or the like and a B site (W site) is replaced by Ta, Nb, Ti, Zr or the like.
(5) Not Less than 39.0 and Less than 55.0 Mass % of Ni
Ni replaces a Co site to generate an L12-type intermetallic compound phase of (Co, Ni)3(Al, W). Moreover, Ni is equally distributed in an matrix Ξ³ phase and the strengthening Ξ³β² phase. In particular, when a Co site of the Ξ³β² phase is replaced by Ni, a solid solution temperature of the Ξ³β² phase is increased and high-temperature strength is improved. In order to obtain the effect, the Ni content needs to be not less than 39.0 mass %. The Ni content is, more preferably, not less than 41.0 mass %, and further preferably, not less than 43.0 mass %.
However, when the Ni content becomes excessive, a melting point of the matrix Ξ³ phase is lowered and hot workability is decreased. Therefore, the Ni content needs to be less than 55.0 mass %. The Ni content is, more preferably, less than 52.0 mass %, and further preferably, less than 50.0 mass %.
In the Co-based alloy according to the invention, Mo, Nb, Ti and Ta among the inevitable impurities particularly need to be within the following ranges.
(6) Less than 0.010 mass % of Mo
Mo functions as a solid solution strengthening element. However, strengthening by Mo is smaller than that by Ta. Moreover, addition of Mo decreases oxidation resistance. Therefore, a Mo content needs to be less than 0.010 mass %.
(7) Less than 0.010 Mass % of Nb
Nb has an effect of improving a high-temperature strength in a Ni-based alloy since Ni3Nb as a Ξ³β³ (Ξ³ double prime) phase is precipitated. However, the Ξ³β³ phase is not precipitated by addition of Nb in a Co-based alloy, thereby resulting in a decrease in hot workability and high-temperature strength due to a lowered melting point. Therefore, the Nb content needs to be less than 0.010 mass %.
(8) Less than 0.010 Mass % of Ti
Ti replaces an Al site of Ni3Al in a Ni-based alloy and is effective for strengthening the Ξ³β² phase. However, an excessive addition of Ti increases a Ξ³β² solid solution temperature and decreases a melting point of a matrix, thereby resulting in a decrease in workability. In a Co-based alloy, an excessive addition of Ti decreases a melting point, thereby resulting in a decrease in hot workability and high-temperature strength. Therefore, the Ti content needs to be less than 0.010 mass %.
(9) Less than 0.010 Mass % of Ta
Ta functions to effect solid-solution strengthening of a Ξ³β² phase, and is effective for improving high-temperature strength. However, high-temperature ductility is significantly decreased by an addition of Ta. As a result, specifically a high-temperature creep rupture property is decreased, since rupture is early generated due to a decrease in ductility. Therefore, a Ta content needs to be less than 0.010 mass %.
In addition to the above elements, the Co-based alloy according to the invention may further include one or more of the following elements. The supplemental additional elements, ranges thereof, and reasons for determining the ranges are as follows.
(10) Not Less than 0.0001 and Less than 0.020 Mass % of Boron
(11) Not Less than 0.0001 and Less than 0.10 Mass % of Zr
Boron and Zr function to strength grain boundaries, and promote to improve hot workability. In order to obtain the effect, a boron content is preferably 0.0001 mass %. In addition, a Zr content is preferably not less than 0.0001 mass %.
However, when the boron or Zr content becomes excessive, workability is decreased in each case. Therefore, the boron content is preferably less than 0.020 mass %. In addition, the Zr content is preferably less than 0.10 mass %.
(12) Not Less than 0.0001 and Less than 0.10 Mass % of Mg
(13) Not Less than 0.0001 and Less than 0.20 Mass % of Ca
Both Mg and Ca fix S and promote to improve hot workability. In order to obtain the effect, a Mg content is preferably not less than 0.0001 mass %. In addition, a Ca content is preferably not less than 0.0001 mass %.
However, when a Mg or Ca content becomes excessive with respect to S, a compound of Mg or Ca is formed, thereby resulting in a decrease in workability. Therefore, the Mg content is preferably less than 0.10 mass %. In addition, the Ca content is preferably less than 0.20 mass %.
When the Co-based alloy according to the invention is subjected to casting, homogenizing heat treatment, hot working, solution treatment and aging treatment under conditions as described below, the Co-based alloy includes a matrix Ξ³ phase, and a carbide and Ξ³β² phase precipitated in the matrix. The Ξ³β² phase is precipitated mainly within grains of the matrix. However, the carbide is precipitated both within the grains and in grain boundaries of the matrix. In order to improve a high-temperature strength, the carbide is preferably precipitated in the grain boundaries. Moreover, in order to suppress grain boundary sliding at a high temperature, a shape of the carbide precipitated in the grain boundaries is preferably granular.
When the Co-based alloy according to the invention after hot working is subjected to solution treatment and aging treatment of various conditions, the Ξ³ phase, the Ξ³β² phase and the carbide for suitable for various purposes can be obtained. The aging treatment is not limited to one-step aging treatment, and may include multiple-step aging treatment of two steps or more.
Firstly, raw materials are prepared so that the above composition of the Co-based alloy is obtained, and are melted and cast. The invention does not limit a melting/casting method and conditions thereof, and various methods and conditions may be used.
Next, obtained ingot is subjected to homogenizing heat treatment (soaking). The homogenizing heat treatment means that for removing solidification segregation generated in the melting/casting process and homogenizing the contents. Hot workability can be improved by the homogenizing.
An optimum temperature is determined depending on the composition of the alloy. Generally, if the homogenizing heat treatment temperature is too low, a diffusion speed of an alloy element becomes slow, and a sufficient effect can not be obtained within a realistic time frame of the heat treatment. Therefore, the homogenizing heat treatment temperature is preferably 1000Β° C. or higher.
However, if the homogenizing heat treatment temperature becomes too high, internal oxidation proceeds and hot workability is decreased. Therefore, the homogenizing heat treatment temperature is preferably 1250Β° C. or lower.
When the alloy is held at a temperature at which the alloy takes a single Ξ³ phase, a heterogenous phase is generally disappeared within several hours and the single Ξ³ phase is obtained. However, a longer time period of the heat treatment is required to remove the solidification segregation generated in the melting/casting process. Generally, as the time for the homogenizing heat treatment becomes long, the contents of the alloy are uniformized and an amount of harmful phase for hot workability can be reduced. In order to reduce a volume ratio of the harmful phase, the time period for the homogenizing heat treatment is preferably 10 hours or longer.
When the Co-based alloy is subjected to the homogenizing heat treatment under predetermined conditions and then cooled, the alloy has the Ξ³ single phase and less harmful phase.
Next, the Co-based alloy after the homogenizing heat treatment is subjected to hot working, and is formed into various shapes. A hot working method and conditions thereof are not specifically limited, and various methods and conditions may be used for any purpose.
Next, the hot-worked Co-based alloy is subjected to solution treatment. The solution treatment is made for solid-soluting precipitates, such as Ξ³β²-phase or carbide, generated during the hot working process. A temperature for the solution treatment is preferably within a range of 1000 to 1250Β° C.
Optimum time period for the solution treatment is determined depending on the solution treatment temperature. Generally, as the solution treatment temperature becomes high, the precipitates can be solid-soluted in a short time.
Next, aging treatment is performed for the Co-based alloy after the solution treatment. By aging the Co-based alloy after the solution treatment in a (Ξ³+Ξ³β²) region, the Ξ³β² phase composed of an L12-type intermetallic compound of Co3(Al, W) can be precipitated in the Ξ³ phase. At the same time, the carbide can be precipitated.
Conditions for the aging treatment are not specifically limited, and optimum conditions are selected depending on the composition of the alloy and/or purpose. Generally, as an aging temperature becomes high, and/or aging time becomes long, the precipitated amount of Ξ³β² phase is increased, or a grain size of the Ξ³β² phase becomes larger. It applies to the carbide.
Usually, the aging temperature is within a range of 500 to 1100Β° C. (preferably, 600 to 1000Β° C.), and the aging time is within a range of 1 to 100 hours, preferably, about 10 to 50 hours.
Multiple-step aging treatment at different temperatures may be employed. By the multiple-step aging treatment, the Ξ³β² phases with different sizes can be precipitated. Generally, large-sized Ξ³β²phase is effective for improving high-temperature properties, in particular, creep rupture property, while it decreases room-temperature properties. In contrast, small-sized Ξ³β² phase is effective for improving room-temperature properties, while it decreases high-temperature properties. Thus, when the Ξ³β² phases with different sizes are precipitated by the multiple-step aging treatment, both of high-temperature and room-temperature properties can be improved at the same time.
For example, in a case where two-step aging treatment is performed, an aging temperature for a first step is preferably in a range of 700 to 1100Β° C., and an aging temperature for a second step is preferably in a range of 500 to 900Β° C.
A Co-based alloy containing Al and W in general generates a phase harmful to hot workability. In particular, excess W generates a harmful phase within grains and in grain boundaries, and hot workability is significantly decreased.
In contrast, a Co-based alloy with less harmful phase can be obtained when it has a predetermined composition (in particular, Al and W contents) and is subjected to a homogenizing heat treatment under predetermined conditions. In addition, Co3(Al, W) strengthening phase (Ξ³β² phase) is precipitated by a solution treatment and an aging treatment under predetermined conditions after the hot working. Furthermore, when a predetermined amount of carbon is added to the Co-based alloy containing predetermined amounts of Al, W and Cr, carbide containing W and/or Cr is precipitated in addition to the Ξ³β² phase after the aging treatment. At this time, granular carbide can be precipitated in the grain boundaries of a matrix Ξ³ phase by optimizing the carbon content. The granular carbide precipitated in the grain boundaries has a large effect of suppressing grain boundary sliding at a high temperature.
That is, a creep rupture property (high-temperature ductility) specifically required for a high-temperature material is remarkably improved in comparison to a conventional Co-based alloy, by precipitating a predetermined amount of carbide in the grain boundaries in addition to the precipitation of the Ξ³β² phase. Accordingly, the Co-based alloy having endurance strength equal to or greater than that of an existing Ni-based alloy can be obtained.
Alloys having compositions shown in Tables 1 and 2 were each melted in a vacuum induction furnace to obtain a 50 kg ingot. Each ingot prepared by melting was subjected to homogenizing heat treatment at 1200Β° C. for 16 hours. Then, the ingot was forged into a rod having a diameter of 16 mm. Solution treatment (ST) was performed for the forged material, under conditions of 1200Β° C. and followed by air cooling for one hour. Then, two-step aging treatment (AG) was performed under conditions of 900Β° C. for 24 hours followed by air cooling, and furthermore, under conditions of 800Β° C. for 24 hours followed by air cooling.
| TABLE 1 | |
| composition (mass %) |
| C | Ni | Co | Cr | W | Al | B | Mg | Zr | Ca | others | |
| Example 1 | 0.020 | 47.6 | Bal | 12.4 | 16.2 | 3.7 | β | β | β | β | β |
| Example 2 | 0.004 | 48.2 | Ba | 12.1 | 15.2 | 3.9 | β | β | β | β | β |
| Example 3 | 0.060 | 46.9 | Bal | 12.3 | 15.4 | 4.1 | β | β | β | β | β |
| Example 4 | 0.020 | 40.1 | Bal | 11.9 | 15.3 | 4.2 | β | β | β | β | β |
| Example 5 | 0.021 | 42.3 | Bal | 12.1 | 16.3 | 3.5 | β | β | β | β | β |
| Example 6 | 0.020 | 51.2 | Bal | 12.1 | 16.0 | 3.4 | β | β | β | β | β |
| Example 7 | 0.016 | 52.5 | Bal | 12.3 | 16.1 | 3.6 | β | β | β | β | β |
| Example 8 | 0.018 | 48.0 | Bal | 9.5 | 15.3 | 3.9 | β | β | β | β | β |
| Example 9 | 0.021 | 47.6 | Bal | 10.3 | 16.3 | 4.1 | β | β | β | β | β |
| Example 10 | 0.022 | 48.2 | Bal | 18.1 | 16.0 | 4.2 | β | β | β | β | β |
| Example 11 | 0.021 | 46.9 | Bal | 18.8 | 16.1 | 3.5 | β | β | β | β | β |
| Example 12 | 0.020 | 45.3 | Bal | 11.9 | 13.8 | 3.4 | β | β | β | β | β |
| Example 13 | 0.019 | 45.0 | Bal | 12.1 | 14.7 | 3.5 | β | β | β | β | β |
| Example 14 | 0.023 | 48.0 | Bal | 12.1 | 18.3 | 3.4 | β | β | β | β | β |
| Example 15 | 0.021 | 45.0 | Bal | 12.3 | 19.5 | 3.6 | β | β | β | β | β |
| Example 16 | 0.020 | 47.6 | Bal | 11.9 | 15.2 | 2.3 | β | β | β | β | β |
| Example 17 | 0.016 | 48.2 | Bal | 12.1 | 15.4 | 2.8 | β | β | β | β | β |
| Example 18 | 0.018 | 46.9 | Bal | 12.1 | 15.3 | 4.4 | β | β | β | β | β |
| Example 19 | 0.022 | 47.6 | Bal | 11.9 | 16.3 | 4.8 | β | β | β | β | β |
| Example 20 | 0.021 | 48.2 | Bal | 12.1 | 16.0 | 3.7 | 0.005 | β | β | β | β |
| Example 21 | 0.020 | 46.9 | Bal | 12.3 | 15.4 | 3.9 | β | 0.005 | β | β | β |
| Example 22 | 0.020 | 48.0 | Bal | 11.9 | 15.3 | 4.1 | β | β | 0.050 | β | β |
| Example 23 | 0.016 | 47.6 | Bal | 12.1 | 16.0 | 4.2 | 0.006 | 0.006 | β | β | β |
| Example 24 | 0.018 | 48.2 | Bal | 12.1 | 15.3 | 3.5 | β | 0.003 | 0.002 | β | β |
| Example 25 | 0.021 | 46.9 | Bal | 12.1 | 16.3 | 4.1 | 0.006 | β | 0.030 | β | β |
| Example 26 | 0.022 | 45.3 | Bal | 13.3 | 16.0 | 4.2 | 0.002 | 0.003 | 0.002 | β | β |
| Example 27 | 0.018 | 46.9 | Bal | 12.1 | 15.3 | 3.5 | β | β | β | 0.030 | β |
| TABLE 2 | |
| composition (mass %) |
| C | Ni | Co | Cr | W | Al | B | Mg | Zr | Ca | others | |
| Comparative | 0.130 | 41.3 | Bal | 14.3 | 16.3 | 3.8 | β | β | β | β | |
| Example 31 | |||||||||||
| Comparative | 0.020 | 47.6 | Bal | 2.5 | 15.4 | 3.7 | β | β | β | β | β |
| Example 32 | |||||||||||
| Comparative | 0.021 | 48.2 | Bal | 22.1 | 16.1 | 3.6 | β | β | β | β | β |
| Example 33 | |||||||||||
| Comparative | 0.020 | 25.2 | Bal | 12.7 | 14.9 | 4.0 | β | β | β | β | β |
| Example 34 | |||||||||||
| Comparative | 0.016 | 60.0 | Bal | 12.3 | 15.3 | 3.9 | β | β | β | β | β |
| Example 35 | |||||||||||
| Comparative | 0.018 | 46.9 | Bal | 12.7 | 10.3 | 4.1 | β | β | β | β | β |
| Example 36 | |||||||||||
| Comparative | 0.021 | 45.3 | Bal | 11.9 | 20.2 | 4.2 | β | β | β | β | β |
| Example 37 | |||||||||||
| Comparative | 0.022 | 45.0 | Bal | 12.1 | 16.1 | 1.8 | β | β | β | β | β |
| Example 38 | |||||||||||
| Comparative | 0.021 | 48.0 | Bal | 12.3 | 16.3 | 5.2 | β | β | β | β | β |
| Example 39 | |||||||||||
| Comparative | 0.020 | 47.5 | Bal | 11.8 | 15.2 | 3.5 | 0.2 | β | β | β | β |
| Example 40 | |||||||||||
| Comparative | 0.019 | 47.8 | Bal | 11.9 | 15.4 | 3.4 | β | 0.2 | β | β | β |
| Example 41 | |||||||||||
| Comparative | 0.023 | 47.3 | Bal | 12.1 | 15.3 | 3.6 | β | β | 0.3 | β | β |
| Example 42 | |||||||||||
| Comparative | 0.021 | 48.2 | Bal | 12.7 | 15.2 | 3.5 | β | β | β | 0.3 | β |
| Example 43 | |||||||||||
| Comparative | β | 47.8 | Bal | 10.1 | 16.3 | 3.2 | β | β | β | β | β |
| Example 44 | |||||||||||
| Comparative | 0.025 | 47.5 | Bal | 11.7 | 16.4 | 3.5 | β | β | β | β | 1.8 Mo |
| Example 45 | |||||||||||
| Comparative | 0.023 | 48.3 | Bal | 11.9 | 15.9 | 3.7 | β | β | β | β | 3.0 Nb |
| Example 46 | |||||||||||
| Comparative | 0.021 | 47.7 | Bal | 11.8 | 16.2 | 3.6 | β | β | β | β | 1.9 Ti |
| Example 47 | |||||||||||
| Comparative | 0.024 | 47.9 | Bal | 11.5 | 15.7 | 3.7 | β | β | β | β | 2.8 Ta |
| Example 48 | |||||||||||
| Comparative | 0.024 | 47.6 | Bal | 10.9 | 14.9 | 3.4 | β | β | β | β | 0.5 Mo |
| Example 49 | |||||||||||
| Comparative | 0.024 | 47.3 | Bal | 11.5 | 14.4 | 3.9 | β | β | β | β | 0.5 Nb |
| Example 50 | |||||||||||
| Comparative | 0.024 | 47.5 | Bal | 12.2 | 15.9 | 4.2 | β | β | β | β | 0.3 Ti |
| Exampe 51 | |||||||||||
| Comparative | 0.024 | 46.7 | Bal | 11.7 | 16.3 | 4.1 | β | β | β | β | 0.6 Ta |
| Example 52 | |||||||||||
A test piece having a test portion with a diameter of 8 mm and a test piece length of 90 mm was cut out from each material. The test piece was subjected to a tensile test at 800Β° C. to measure 0.2% yield stress and tensile strength.
A test piece having a parallel portion of 30 mm and a test piece length of 92.6 mm was cut out from each material. A creep rupture test was performed under conditions of 800Β° C. and 294 MPa for the test piece to measure a rupture life, and elongation and reduction when rupturing.
A rectangular test piece having a size of 13 mmΓ25 mm and a thickness of 2 mm was cut out from each material. The test piece was continuously heated at 800Β° C. in an air atmosphere for 200 hours, and then was air cooled. A weight increase by oxidation was calculated from a weight difference between before and after the test, and was used as an index of oxidation resistance.
The results are shown in Tables 3 and 4.
(1) Among Comparative Examples 31 to 52, the specimens which could be forged had low strength and high-temperature ductility.
(2) Each of Examples 1 to 27 exhibits high strength at 800Β° C., and has 0.2% yield stress of 700 MPa or greater and tensile strength of 850 MPa or greater. Moreover, each specimen has elongation of 10% or greater, which representing high-temperature ductility.
(3) Comparative Example 44 does not substantially contain carbon and has low tensile strength and elongation. This is because strengthening of grain boundary by carbide was not effected and rupture was early generated from the grain boundaries.
(1) Among Comparative Examples 31 to 52, specimens which could be forged had a short rupture life and poor high-temperature ductility.
(2) Each of Examples 1 to 27 had a rupture life of 1000 hours or longer, and had high elongation of 10% or greater and reduction of 20% or greater.
(3) Comparative Example 44 does not substantially contain carbon and has a short rupture life and low elongation and reduction. This is because strengthening of grain boundary by carbide was not effected and rupture was early generated, as the case of high-temperature tensile property.
FIGS. 1 and 2 show microstructures of a ruptured portion of the Co-based alloy (Example 1) before and after the creep rupture test. In the microstructure before the creep rupture test, the Ξ³β² phases precipitated in cubic or spherical grains are linked (raft structure) at a high-temperature and under a high stress. Moreover, precipitation of the carbide mainly containing W and Cr is observed in the grain boundaries. Since this is not observed in the microstructure after the test in the comparative examples, it is thought that high-temperature ductility behavior in the creep rupture test is closely related to the structural change of the Ξ³β² phase and the precipitation of the carbide in the grain boundaries.
(1) The weight increase by oxidation of the Co-based alloy is influenced by the Al and Cr contents. Since Comparative Example 38 has a lower Al content, oxidation resistance was decreased. In addition, Comparative Example 32 having a lower Cr content was impossible to be forged mainly due to grain boundary oxidation.
(2) Examples 1 to 27 exhibit excellent oxidation resistance.
| TABLE 3 | ||||
| 800Β° C. oxidation |
| 800Β° C. | property, |
| 0.2% | tensile | 800Β° C.-294 MPa | weight increase |
| yield stress | strength | elongation | rupture life | elongation | reduction | by oxidation | |
| (MPa) | (MPa) | (%) | (H) | (%) | (%) | (mg/cm2) | |
| Example 1 | 770 | 990 | 17.0 | 1450 | 14.1 | 28.0 | 0.20 |
| Example 2 | 752 | 954 | 15.8 | 1075 | 13.6 | 25.3 | 0.23 |
| Example 3 | 766 | 976 | 15.3 | 1296 | 12.5 | 26.4 | 0.21 |
| Example 4 | 714 | 878 | 16.6 | 1105 | 13.3 | 27.3 | 0.27 |
| Example 5 | 737 | 942 | 16.8 | 1362 | 13.5 | 27.8 | 0.23 |
| Example 6 | 763 | 971 | 16.8 | 1398 | 13.4 | 27.9 | 0.21 |
| Example 7 | 749 | 954 | 16.7 | 1287 | 13.3 | 27.4 | 0.20 |
| Example 8 | 737 | 882 | 13.6 | 1003 | 11.3 | 23.6 | 0.41 |
| Example 9 | 760 | 940 | 15.2 | 1298 | 12.4 | 25.8 | 0.32 |
| Example 10 | 735 | 923 | 14.5 | 1302 | 12.3 | 24.8 | 0.15 |
| Example 11 | 720 | 895 | 14.3 | 1192 | 11.6 | 23.6 | 0.13 |
| Example 12 | 732 | 863 | 16.9 | 1153 | 13.8 | 27.7 | 0.19 |
| Example 13 | 751 | 938 | 16.6 | 1303 | 13.9 | 28.1 | 0.21 |
| Example 14 | 768 | 987 | 12.3 | 1285 | 12.4 | 26.1 | 0.23 |
| Example 15 | 765 | 993 | 11.5 | 1039 | 11.1 | 24.3 | 0.26 |
| Example 16 | 719 | 905 | 16.9 | 1263 | 13.8 | 27.3 | 0.31 |
| Example 17 | 732 | 932 | 17.1 | 1324 | 14.0 | 27.5 | 0.25 |
| Example 18 | 758 | 970 | 16.5 | 1290 | 13.8 | 28.1 | 0.17 |
| Example 19 | 739 | 950 | 15.9 | 1156 | 13.6 | 27.6 | 0.15 |
| Example 20 | 772 | 989 | 17.3 | 1398 | 14.7 | 29.0 | 0.23 |
| Example 21 | 763 | 982 | 17.5 | 1432 | 15.0 | 28.8 | 0.21 |
| Example 22 | 771 | 993 | 18.1 | 1440 | 14.9 | 29.1 | 0.24 |
| Example 23 | 767 | 985 | 18.2 | 1486 | 15.1 | 29.3 | 0.20 |
| Example 24 | 765 | 983 | 17.8 | 1430 | 14.8 | 28.6 | 0.28 |
| Example 25 | 769 | 987 | 17.6 | 1462 | 14.9 | 28.9 | 0.26 |
| Example 26 | 773 | 993 | 17.5 | 1442 | 14.6 | 28.8 | 0.25 |
| Example 27 | 769 | 978 | 16.9 | 1438 | 14.6 | 27.8 | 0.21 |
| TABLE 4 | ||||
| 800Β° C. oxidation |
| 800Β° C. | property, |
| 0.2% | tensile | 800Β° C.-294 MPa | weight increase |
| yield stress | strength | elongation | rupture life | elongation | reduction | by oxidation | |
| (MPa) | (MPa) | (%) | (H) | (%) | (%) | (mg/cm2) | |
| Comparative | 656 | 743 | 8.1 | 786 | 7.2 | 18.3 | 0.23 |
| Example 31 |
| Comparative | forging impossible |
| Example 32 | |||||||
| Comparative | 689 | 793 | 11.2 | 876 | 10.3 | 18.0 | 0.11 |
| Example 33 | |||||||
| Comparative | 532 | 588 | 16.3 | 678 | 13.2 | 20.3 | 0.28 |
| Example 34 | |||||||
| Comparative | 651 | 690 | 3.5 | 869 | 2.9 | 7.0 | 0.25 |
| Example 35 | |||||||
| Comparative | 532 | 638 | 15.3 | 863 | 13.9 | 27.5 | 0.22 |
| Example 36 |
| Comparative | forging impossible |
| Example 37 | |||||||
| Comparative | 541 | 672 | 14.6 | 859 | 15.2 | 23.1 | 0.71 |
| Example 38 | |||||||
| Comparative | 499 | 527 | 2.6 | 537 | 1.7 | 3.9 | 0.15 |
| Example 39 |
| Comparative | forging impossible |
| Example 40 |
| Comparative | forging impossible |
| Example 41 |
| Comparative | forging impossible |
| Example 42 |
| Comparative | forging impossible |
| Example 43 | |||||||
| Comparative | 651 | 690 | 3.5 | 520 | 2.9 | 7.0 | 0.22 |
| Example 44 |
| Comparative | forging impossible |
| Example 45 |
| Comparative | forging impossible |
| Example 46 |
| Comparative | forging impossible |
| Example 47 |
| Comparative | forging impossible |
| Example 48 | |||||||
| Comparative | 683 | 723 | 5.3 | 685 | 3.3 | 8.8 | 0.53 |
| Example 49 | |||||||
| Comparative | 698 | 743 | 3.1 | 685 | 3.2 | 8.4 | 0.27 |
| Example 50 | |||||||
| Comparative | 710 | 751 | 7.6 | 679 | 3.1 | 8.7 | 0.33 |
| Example 51 | |||||||
| Comparative | 702 | 743 | 8.7 | 874 | 8.3 | 12.2 | 0.23 |
| Example 52 | |||||||
While the embodiment of the invention was described in detail above, the invention is not limited to the above embodiment, and various modifications may be made without departing from the spirit and scope of the invention.
The Co-based alloy according to the invention can be used for various components required to have a high strength in a high-temperature environment, such as a gas turbine component, an aircraft engine component, a chemical plant component, a vehicle engine component or a high-temperature furnace component.
1. A Co-based alloy comprising:
not less than 0.001 and less than 0.100 mass % of C;
not less than 9.0 and less than 20.0 mass % of Cr;
not less than 2.0 and less than 5.0 mass % of Al;
not less than 13.0 and less than 20.0 mass % of W;
not less than 39.0 and less than 55.0 mass % of Ni; and
the balance being Co and inevitable impurities, wherein the impurities include
less than 0.010 mass % of Mo,
less than 0.010 mass % of Nb,
less than 0.010 mass % of Ti, and
less than 0.010 mass % of Ta.
2. The Co-based alloy according to claim 1, further comprising at least one of
not less than 0.0001 and less than 0.020 mass % of B and
not less than 0.0001 and less than 0.10 mass % of Zr.
3. The Co-based alloy according to claim 1, further comprising at least one of
not less than 0.0001 and less than 0.10 mass % of Mg and
not less than 0.0001 and less than 0.20 mass % of Ca.
4. The Co-based alloy according to claim 1, produced through hot working, solution treatment and aging treatment, the alloy
comprising a Ξ³ phase matrix, carbide precipitated in the matrix, and a Ξ³β² phase composed of an L12-type intermetallic compound.