Patent Application
20190194789
The present application claims priority from Japanese patent application serial no. 2017-249052 filed on Dec. 26, 2017, the content of which is hereby incorporated by reference into this application.
The present invention relates to precipitation-strengthened nickel-based alloy members for use such as high-temperature members in turbines and, in particular, to a nickel-based alloy regenerated member and a method for manufacturing the regenerated member. The regeneration involves extending the useful service life of an alloy member creep-damaged after having operated for long hours in a high-temperature environment.
High-temperature members for use in thermal power generation plants and aircraft turbines, such as turbine blades and rotors, are often made of precipitation-strengthened nickel (Ni)-based alloys (also referred to as nickel-based super alloys) to satisfy the mechanical properties required of them to operate in high-temperature environments.
Unfortunately, however, even such Ni-based alloy members with excellent high-temperature strength gradually deteriorate in their mechanical properties after being repeatedly exposed to the centrifugal force during operation at a high temperature and the thermal stress during start-up and shut-down operations. In particular, the creep strength of such members is most severely affected, which consumes its service life as the operation time increases. It is noted that any consumption of creep-strength life can be referred to as creep damage.
Today, in general, from the viewpoint of improving the rate of turbine utilization (i.e. avoiding the risk of halting due to an unexpected breakdown), any high-temperature member having operated for a predetermined period of time is replaced with a new one at regular inspection intervals assuming that it is creep-damaged to some extent.
Meanwhile, there is a technical trend in turbines toward higher inlet gas temperature for improving thermal efficiency. In recent years, vigorous research and development has been carried out on techniques for improving heat resistance of high-temperature members for use in turbines (e.g. addition of rare metal elements for improved high-temperature strength and solidification/crystal growth controlling techniques). Unfortunately, high-temperature members manufactured through such sophisticated techniques tend to be expensive, and the necessity of member replacement at regular inspection intervals increases turbine maintenance cost.
There is, quite naturally, a strong demand for low-cost industrial products. So, what is needed is to concurrently achieve higher performance and lower cost. Therefore, one solution under consideration is to develop a technique to increase the precision of life assessment of creep-damaged high-temperature members in order to reduce the replacement frequency of high-temperature members.
For example, JP 2010-164430 A discloses a metal material creep damage evaluation method for evaluating a degree of damage to a creep-damaged metal material. In this method, a correlation between the amount of creep strain of a test material and the crystal orientation distribution of the material is determined in advance. The crystal orientation distribution of a subject material of creep damage evaluation is measured. The measured crystal orientation distribution of the subject material is applied to the correlation between the amount of creep strain and the crystal orientation distribution to estimate the amount of creep strain of the subject material. Another correlation between the amount of strain at which the test material reaches an accelerated creep stage and creep test stress is determined in advance. The amount of strain at which the subject material reaches an accelerated creep stage is estimated from the stress loaded to the subject material and the correlation between the amount of strain at which the test material reaches an accelerated creep stage and creep test stress. The degree of damage to the subject material is evaluated by comparing the estimated amount of creep strain of the subject material with the estimated amount of strain at which the subject material reaches an accelerated creep stage.
Also, JP 2014-126442 A discloses a nickel-based superalloy degradation diagnosis method. In this method, a nickel-based superalloy is subjected to a heat treatment under conditions that satisfy a relationship defined by a predetermined formula between heat treatment temperature and heat treatment duration. Subsequently, the presence of a crystal caused by recrystallization in the nickel-based superalloy is measured.
According to JP 2010-164430 A, there can be provided a metal material creep damage evaluation method and a creep damage evaluation apparatus that allow highly accurate and stable evaluation of the appropriateness of continuous use of metal materials. According to JP 2014-126442 A, the prior art has been made based on the finding that a nickel-based superalloy that has reached its service life limit can be led to recrystallization by subjecting it to a predetermined heat treatment, and the method provided uses a simple degradation diagnosis method and allows accurate degradation diagnosis.
To further reduce turbine maintenance cost, it would be preferable to recycle creep-damaged members as regenerated members through their life extension or regeneration in addition to assessing their service life. While the techniques disclosed in JP 2010-164430 A and JP 2014-126442 A can be expected to allow simple and high-precision life assessment of Ni-based high-temperature members, no description can be found in the two as to any technique for life extension or regeneration of creep-damaged members.
In view of the foregoing, it is an objective of the present invention to provide an Ni-based alloy regenerated member that is obtained by extending the useful service life of a creep-damaged Ni-based alloy member and a method for manufacturing the regenerated member.
(I) According to one aspect of the present invention, there is provided a method for manufacturing a regenerated member of a nickel-based alloy member for use in a turbine. The nickel-based alloy member is a nickel-based alloy unidirectional solidification article or single crystalline solidification article including a γ phase as a matrix and a γ′ phase precipitating in the γ phase in a volume fraction of equal to or more than 30 volume % in an operational environment of the turbine. The method includes: a solution/non-recrystallization heat treatment step of subjecting a used member to a solution/non-recrystallization heat treatment, the used member being the nickel-based alloy member having operated for a predetermined period of time in the turbine; and an aging heat treatment step of subjecting the used member having undergone the solution/non-recrystallization heat treatment to an aging heat treatment to allow the γ′ phase to precipitate in the γ phase. In the solution/non-recrystallization heat treatment, the used member is held at a temperature that is equal to or higher than a temperature higher than the solvus temperature of the γ′ phase by 10° C. but equal to or lower than a temperature lower than the melting temperature of the γ phase by 10° C., for a holding duration within a time range in which recrystallized grains of the γ phase do not generate. And, when a rocking curve of a predetermined crystal face of the γ phase crystal grain of the used member undergone the solution/non-recrystallization heat treatment step is measured by an X-ray diffraction (XRD) technique, a full width at half maximum (FWHM) of the rocking curve is equal to or more than 0.25° and equal to or less than 0.30°.
Meanwhile, in the present invention, each of the solvus temperature of γ′ phase and the melting temperature (solidus temperature) of γ phase may be assumed a calculated value based on a chemical composition of the nickel-based alloy by a thermodynamic calculation.
In the above aspect (I) of a method for manufacturing a regenerated member of a nickel-based alloy member for use in a turbine, the following modifications and changes can be made.
(i) The holding duration in the solution/non-recrystallization heat treatment step may be equal to or more than 15 minutes and equal to or less than 2 hours.
(ii) The predetermined crystal face may be a {h00}γ-phase plane of the γ phase crystal grain.
(iii) The {h00}γ-phase plane of the γ phase crystal grain may be a {200}γ-phase plane.
(iv) The nickel-based alloy member may be a turbine blade.
(II) According to another aspect of the invention, there is provided a regenerated member of a nickel-based alloy member for use in a turbine. The nickel-based alloy member had been creep-damaged by being used in the turbine for a predetermined period of time, i.e. being a used member. The regenerated member is a nickel-based alloy unidirectional solidification article or single crystalline solidification article including a γ phase as a matrix and a γ′ phase precipitating in the γ phase in a volume fraction of equal to or more than 30 volume % in an operational environment of the turbine. In a microstructure of the regenerated member, no recrystallized grains of the γ phase are present. And, when a rocking curve of a predetermined crystal face of the γ phase crystal grain of the used member undergone the solution/non-recrystallization heat treatment step is measured by an XRD technique, a FWHM of the rocking curve is equal to or more than 0.25° and equal to or less than 0.30°.
In the above aspect (II) of a regenerated member of a nickel-based alloy member for use in a turbine, the following modifications and changes can be made.
(v) The regenerated member may have a creep life of equal to or more than 0.95 when the nickel-based alloy member has a creep life of 1 when it is in an unused condition, i.e. being a virgin member.
(vi) The predetermined crystal face may be a {h00}γ-phase plane of the γ phase crystal grain. vii) The {h00}γ-phase plane of the γ phase crystal grain may be a {200}γ-phase plane.
(viii) The nickel-based alloy member may be a turbine blade.
According to the present invention, there can be provided an Ni-based alloy regenerated member that is obtained by extending the useful service life of a creep-damaged Ni-based alloy member and a method for manufacturing the regenerated member. Also, by using the regenerated member as a high-temperature member for use in turbines, turbine maintenance cost (especially the procurement cost of new high-temperature members) can be reduced.
(Basic Idea of the Invention)
The present invention is directed toward cast articles for precipitation-strengthened Ni-based alloy members for use as high-temperature members in turbines and, in particular, toward Ni-based alloy members having a chemical composition including a γ phase as a matrix and a γ′ phase as a precipitation-strengthening phase (e.g. Ni3Al phase) precipitating in the γ phase in a volume fraction of 30 volume % or more (preferably 40 to 70 volume %). That is, the Ni-based alloy member has a chemical composition in which the γ′ phase at a ratio of 30 volume % or more can be precipitated. And, the Ni-based alloy member is formed of a unidirectional solidification article or a single crystalline solidification article.
The inventors carried out intensive study and research on techniques to evaluate the degree of creep damage and the influence of heat treatment on creep-damaged members with an aim to develop an Ni-based alloy regenerated member obtained by extending the useful service life of a creep-damaged Ni-based alloy member. As a result, the inventors found that there is a close relationship among the degree of creep damage, the degree of internal strain of γ phase crystal grains, and the occurrence of γ phase recrystallized grains in a heat treatment on a creep-damaged member. The inventors also found that creep life can be recovered to 95% or more by partially relaxing the internal strain of γ phase crystal grains while preventing the generation of γ phase recrystallized grains. The invention was made based on these findings.
Preferred embodiments of the present invention will be described hereinafter with reference to the accompanying drawings. However, it should be noted that the invention is not limited to the specific embodiments described below, and various combinations with known art and modifications based on known art are possible without departing from the spirit and scope of the invention where appropriate.
[Experimental 1]
(Fabrication of Alloy Member 1)
A simulation sample of a high-temperature member for turbines according to an embodiment of the invention was Prepared. First, a master ingot of an alloy 1 having a nominal chemical composition as shown in Table 1 was subjected to high-frequency melting. Subsequently, a cast plate article (200 mm long, 200 mm wide, and 10 mm thick) was fabricated by a unidirectional solidification method. The solvus temperature of the γ′ phase in the alloy 1 is approximately 1,190° C.
The unidirectional solidification plate article prepared above was subjected to a solution heat treatment (held at 1,210° C. for two hours and then rapidly cooled under a vacuum), a 1st step aging heat treatment (held at 1,100° C. for four hours and rapidly cooled under a vacuum), and a 2nd step aging heat treatment (held at 850° C. for ten hours and then rapidly cooled under a vacuum) in succession to fabricate a simulation specimen of a high-temperature member for turbines (Alloy Member 1).
[Experimental 2]
(Preparation of Used Member Specimens, and Evaluation of Degree of Creep Damage and Internal Strain of γ Phase Crystal Grains)
From Alloy member 1, a plurality of creep test pieces (9 mm in diameter and 100 mm in length) were taken such that the unidirectional solidification direction was the longitudinal direction. Subsequently, each of the creep test pieces was subjected to a creep test (900° C., 245 MPa).
In one test, the creep life (tv) of a test piece as a specimen of a virgin member was measured, and it was found to be approximately 950 hours. In other tests, each creep test piece was taken out when it reached a predetermined amount of creep strain (a strain of 0.8% to 2.6%) to serve as a specimen of a used member. Also, the degree of creep damage at each predetermined amount of damage was calculated from the ratio between the time required to reach the amount of creep strain (tc) and the tv (tc/tv). Note that a plurality of creep test pieces were used in each test.
Meanwhile, it was difficult to prepare a specimen in which the amount of strain had been accurately controlled in the region where the amount of creep strain was more than 2.6%. This is considered because the region more than 2.6% of creep strain belongs to the accelerated tertiary creep region.
In order to evaluate internal strain of the γ phase crystal grain of the new member and used member specimens prepared above, a rocking curve of a {200}γ-phase plane of the γ phase crystal was measured by an X-ray diffraction (XRD) technique, and a full width at half maximum (FWHM) of the rocking curve was obtained. There is no specific limitation in a crystal face whose rocking curve is to be measured. It is preferable that a {h00}γ-phase plane be chosen as a crystal face to be measured since the γ phase crystal has a face-centered cubic (fcc) structure; and high intensity X-ray diffraction can be easily obtained. Specifically, the {200}γ-phase plane is more preferable as a crystal face to be measured.
Table 2 shows a relationship among the amount of creep strain, the degree of creep damage, and the full width at half maximum (FWHM) of the rocking curve of the {200}γ-phase plane in this experiment.
As shown in Table 2, there is an apparent correlation in which the degree of creep damage and the FWHM of the rocking curve of the {200}γ-phase plane increase as the amount of creep strain increases. Also, as shown in
[Experimental 3]
(Fabrication of Regenerated Member Sample, Study of Generation Behavior of γ Phase Recrystallized Grains, and Study of Creep Life of Regenerated Member)
Each of the used member specimens prepared in Experimental 2 was subjected to a solution heat treatment (held at 1,200° C. for two hours and then rapidly cooled under a vacuum) as a simulated life extension/regeneration treatment. Subsequently, the metallographic structure (microstructure) of each specimen was observed.
The results showed that no particular change in microstructure was observed in the specimens with a creep strain amount of equal to or less than 1.2%. In contrast, in the specimens with a creep strain amount of 1.3 to 1.5%, generation of γ phase recrystallized grains was observed, and it was also observed that the number and size of the y phase recrystallized grains increased as the amount of creep strain increased. Generation of γ phase recrystallized grains was also observed in the samples with a creep strain amount of over 1.5%, but its degree was about the same as that in the specimens with a creep strain amount of 1.5%, which made it difficult to find any clear difference between the two.
Next, each specimen, which had undergone the solution heat treatment, was subjected to the 1st step aging heat treatment and the 2nd step aging heat treatment the same as those in Experimental 1 to fabricate a regenerated member specimen. The regenerated member specimens thus obtained were each subjected to a creep test in the same manner as Experiment 2 to measure the creep life (tr) of each regenerated member specimen. Also, the ratio between the tr of the regenerated member specimen and the tv of the virgin member specimen (tr/tv) was determined as the degree of regeneration. The results are shown in Table 3.
As shown in Table 3, it is observed that the creep life of the specimens with a creep strain amount of 1.2% or less, in which no particular change in microstructure had been observed after the solution heat treatment, is successfully extended to a degree of regeneration of equal to or more than 0.95 by the heat treatments described above. In contrast, it turns out that the degree of regeneration of the specimens with a creep strain amount of 1.3% or more (i.e. the specimens in which γ phase recrystallized grains had generated due to the solution heat treatment) is insufficient. As for the specimens with a creep strain amount of 1.4% or more, in particular, the creep life of the regenerated part tr is below the original remaining creep life (tv−tc). In other words, it is found that the creep life is shortened by the solution heat treatment.
Next, preferable conditions of the solution heat treatment were studied for the specimens with a creep strain amount of 1.5% or more (with a degree of creep damage of 0.5 or more). Specifically, regenerated member specimens were fabricated under the same conditions as above except for the holding duration in the solution heat treatment, and the degree of regeneration was studied. The results are shown in Table 4.
The results shown in Table 4 are surprising. Even with the specimens with a creep strain amount of 1.5% or more, with which life extension/regeneration was difficult by the above-described solution heat treatment (held at 1,200° C. for two hours under a vacuum and then rapidly cooled), life extension/regeneration is achieved to a degree of regeneration of 0.95 or more by shortening the holding duration of the solution heat treatment.
Specifically, life extension/regeneration is achieved to a degree of regeneration of 0.95 or more when the holding duration for the specimens with a creep strain amount of 1.5% (the specimens with a degree of creep damage of 0.5) is set at one hour; the holding duration for the specimens with a creep strain amount of 2% (the specimens with a degree of creep damage of 0.64) is set at 30 minutes; and the holding duration for the specimens with a creep strain amount of 2.6% (the specimens with a degree of creep damage of 0.75) is set at 15 minutes.
The microstructure observation of the specimens regenerated to a degree of regeneration of 0.95 or more has revealed that no γ phase recrystallized grain has been generated in each specimens. Also, with regard to the specimens having the degree of regeneration of 0.95 or more, the FWHM of the rocking curve of the {200}γ-phase plane of the γ phase crystal grain was measured by the XRD technique; and it has revealed that the FWHM is within a range of 0.25° to 0.30° in all of the specimens.
According to
Meanwhile, when measuring the FWHM of the rocking curve of the {200}γ-phase plane of the γ phase crystal grains with regard to the specimens in which a recrystallized grain had been generated by the solution heat treatment, the FWHM values within a range of 0.23° to 0.26° were obtained, which was equivalent to the FWHM value of a virgin member. This suggests that there are γ phase crystal grains whose internal strain has been fully relaxed.
The mechanism behind the results shown in Tables 3 and 4 is not clarified yet, but it may be explained by the following model.
It could be said that creep strain is accumulated as internal strain of crystal grains. The internal strain of crystal grains tries to relax itself during a solution heat treatment (i.e. it takes to work itself as a driving force for recrystallization to occur). Furthermore, since the occurrence of recrystallization here is thought to be a kind of homogeneous nucleation, it can be considered that it has a higher potential barrier than that of heterogeneous nucleation and requires a larger driving force (i.e. the nucleation frequency is low).
The results shown in Tables 3 and 4 indicate that recrystallized grains are more likely to generate in the specimens with larger creep strain and in a shorter period of time in the heat treatment, which can roughly be explained by this model. Also, it is thought that the creep life of the specimens in which recrystallization has occurred is short after regeneration because generation of recrystallized grains, which leads to formation of new grain boundaries, is not desirable in a unidirectional solidification article or a single crystalline solidification article from the viewpoint of creep properties.
From the series of experiments, an important technical finding was made that in order to regenerate a creep damaged Ni-based alloy member, it is crucial to perform a solution/non-recrystallization heat treatment that partially relaxes the internal strain of the γ phase crystal grains while preventing generation of γ phase recrystallized grains in a solution heat treatment to dissolve the γ′ phase of the creep damaged member in solid solution. From the viewpoint of relaxing the internal strain of the γ phase crystal grains, it is believed that the heat treatment should preferably be performed as long as possible within a time range in which recrystallization does not occur.
Also, from the results shown in Table 4, it is found that a degree of creep damage of 0.5 or more can be determined more clearly than with conventional techniques, based on the holding duration of the solution heat treatment performed on a creep damaged member at which y phase recrystallized grains start to generate, even for alloy members that are expected to have a degree of creep damage of 0.5 or more but whose amounts of creep strain are difficult to directly measure (e.g. members having complicated shapes and members whose amounts of creep strain vary depending on the portions therein). This could be used as a technique/method for evaluating a degree of creep damage.
Furthermore, as shown in
[Experimental 4]
(Reproducibility Verification Experiment Using Alloy Members Formed of Alloys 2 and 3)
Alloy members 2 and 3 were fabricated from Alloys 2 and 3 having the nominal chemical compositions shown in Table 5 below and subjected to the same experiments as Experimentals 2 and 3 except that the temperature of the solution heat treatment for regeneration was set at 1,250° C. The results obtained were similar to those above.
In other words, it is confirmed that in order to regenerate a creep damaged Ni-based alloy member, it is crucial to perform a solution/non-recrystallization heat treatment that partially relaxes the internal strain of the γ phase crystal grains while preventing generation of γ phase recrystallized grains in a solution heat treatment to dissolve the γ′ phase of the creep damaged member in solid solution.
Note that although Experimentals 1 to 4 were conducted on unidirectional solidification articles, the present invention is also applicable to single crystalline solidification articles.
[Method for Manufacturing Regenerated Member]
Based on the technical knowledge made by Experimentals 1 to 4 above, a method for manufacturing an Ni-based alloy regenerated member according to an embodiment of the invention will hereinafter be described.
Next, a solution/non-recrystallization heat treatment step (STEP 2: S2) is conducted. In this step, the used member having undergone the preliminary preparation step S1 is subjected to a solution/non-recrystallization heat treatment. In the solution/non-recrystallization heat treatment, the used member is held at a temperature at least 10° C. higher than the solvus temperature of the y′ phase but not higher than a temperature that is 10° C. lower than the melting point of the γ phase for a period of time within a time range in which γ phase recrystallized grains do not generate. As mentioned before, the largest feature of the present invention lies in this solution/non-recrystallization heat treatment step S2.
The temperature of the solution/non-recrystallization heat treatment is set to a temperature at least 10° C. higher than the solvus temperature of the γ′ phase in order to fully dissolve the γ′ phase in solid solution into the γ phase. Also, the temperature of the heat treatment is set to a temperature that is 10° C. lower than the melting point of the γ phase in order to prevent undesired deformation of the used member during the heat treatment. From the viewpoint of preventing generation of γ phase recrystallized grains, the upper limit temperature of the heat treatment is preferably set to a temperature that is 20° C. lower than the melting point of the γ phase. The reason why the holding duration of the heat treatment is set to be within a time range in which γ phase recrystallized grains do not generate is as described in Experimental 3 above.
Now, how to find out the holding duration with which γ phase recrystallized grains do not generate will briefly be described. If the Ni-based alloy member for use in turbines is a turbine blade, for example, it is considered that a plurality of used members, i.e. used turbine blades, occur at a regular inspection, and they are similarly creep-damaged.
In such a case, a plurality of test pieces for a solution/non-recrystallization heat treatment are taken from one of the used members. Then, using these test pieces, a solution/non-recrystallization heat treatment test is conducted with the holding duration as a parameter. The appropriate holding duration can be determined through microstructure observation of the test pieces.
Also, it is preferable that the FWHM of the rocking curve of the {200}γ-phase plane of γ phase crystal in the test pieces having undergone the solution/non-recrystallization heat treatment test be measured by XRD technique. Measuring the FWHM values makes it possible to confirm that the internal strain of the γ phase crystal grains has been partially relaxed, thereby allowing quality check of the regenerated member in advance. Note that the measurement of the FWHM values (i.e. the confirmation of partial relaxation of the internal strain of the γ phase crystal grains) may be conducted after the aging heat treatment described below.
After the appropriate holding duration in the solution/non-recrystallization heat treatment is determined, the solution/non-recrystallization heat treatment is performed on the other used members.
Next, the used members having undergone the solution/non-recrystallization heat treatment step S2 are subjected to an aging heat treatment step (Step 3: S3). In this step, an aging heat treatment is performed to allow the γ′ phase to precipitate in the γ phase. As this aging heat treatment, the same aging heat treatment as that performed in the manufacturing of a virgin member of the alloy member may preferably be employed.
Subsequently, the used members having undergone the aging heat treatment step S3 are subjected to a finishing/inspection step (Step 4: S4). In this step, finishing work and visual inspection are conducted to finish them as regenerated members. This step is not essential, but it is preferable that it be performed. The finishing work includes shape correction and TBC application, where appropriate.
Through the steps above, Ni-based alloy regenerated members can be obtained.
[Ni-based Alloy Regenerated Member]
The invention is not limited to the above described embodiments, and various modifications can be made. Also, the above embodiments are given for the purpose of detailed illustration and explanation only, and the invention is not intended to include all features and aspects of the embodiments described above. Also, a part of an embodiment may be replaced by known art, or added with known art. That is, a part of an embodiment of the invention may be combined with known art and modified based on known art.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2017-249052 | Dec 2017 | JP | national |
