Patent Application
20160349115
The present invention relates to a temperature estimation method of a high temperature member, a content estimation method of a tetragonal-prime phase, and a deterioration determination method.
This application is based on and claims priority from Japanese Patent Application No. 2014-229619 filed on Nov. 12, 2014, the contents of which are incorporated herein by reference.
In an industrial gas turbine, the demand for high efficiency and high temperature resistance is rapidly increasing, and the importance of a thermal barrier coating (TBC) provided to a high temperature member is also increasing. For example, in order to secure reliability of the TBC, a technique for estimating a surface temperature of the TBC exposed to high temperatures is desired. For example, PTL 1 discloses a temperature estimation method for estimating the amount of an M phase (monoclinic phase) included in a TBC using X-ray diffraction and calculating a surface temperature of the TBC based on the measured amount of monoclinic phase.
The TBC is configured by tough crystals called a T′ phase (tetragonal-prime phase) in an initial stage. However, if the TBC is exposed at a certain high temperature for a long period of time, the T′ phase of the TBC is decomposed into a T phase (tetragonal phase) and a C phase (cubic phase). Then, if the TBC is cooled, the T phase (tetragonal phase) is converted into an M phase (monoclinic phase) to cause volume expansion and reduce fracture toughness. The method disclosed in PTL 1 is a temperature estimation method based on the content of the monoclinic phase (M phase).
[PTL 1] Japanese Patent No. 3519703
It is known that the reason why the T′ phase is decomposed into the T phase and the C phase in such a crystalline structure change process is greatly related to temperature. The method disclosed in PTL 1 is based on the content of the monoclinic phase (M phase) generated after the temperature of the TBC is lowered, but in consideration of the content of the T′ phase, it is considered that if it is possible to check the degree of decomposition of the T′ phase included in the TBC, and to estimate the temperature based on the content of the T′ phase, the surface temperature of the TBC can be estimated more precisely. However, such a temperature estimation method has not been proposed up to now.
The invention provides a temperature estimation method, a content estimation method of a tetragonal-prime phase, and a deterioration determination method capable of solving the above-mentioned problems.
According to a first aspect of the invention, there is provided a temperature estimation method including the steps of: measuring a content of a tetragonal-prime phase included in a coating layer formed on a surface of a high temperature member by X-ray diffraction or Raman spectroscopy; and estimating a surface temperature of the high temperature member based on the estimated content of the tetragonal-prime phase.
According to a second aspect of the invention, the above-described temperature estimation method includes the steps of: performing Rietveld analysis with respect to each of diffraction results obtained by performing measurement based on the X-ray diffraction with respect to a plurality of test members of the coating layer heated at each of a plurality of predetermined heating temperatures for a plurality of predetermined heating times and a diffraction result obtained by performing measurement based on the X-ray diffraction with respect to a member for which contents of a tetragonal-prime phase, a tetragonal phase, and a cubic phase are known in advance to calculate the content of the tetragonal-prime phase included in each of the plurality of test members, accumulating data on a heating temperature, a heating time, and the content of the tetragonal-prime phase corresponding to each test member, and calculating a relational expression between the heating time, the heating temperature, and the content of the tetragonal-prime phase for the test member; performing, when the heating time in the heating is known with respect to a measurement member of the coating layer heated at a heating temperature of a predetermined temperature or higher, the Rietveld analysis with respect to the diffraction results based on the X-ray diffraction with respect to the measurement members and the diffraction result based on the X-ray diffraction with respect to the member for which the contents of the tetragonal-prime phase, the tetragonal phase, and the cubic phase are known in advance to calculate the content of the tetragonal-prime phase included in each measurement member; and calculating the heating temperature of the measurement member based on the heating time of the measurement member, the calculated content of the tetragonal-prime phase included in the measurement member, and the relational expression.
According to a third aspect of the invention, the above-described temperature estimation method includes the steps of: performing Rietveld analysis with respect to each of diffraction results obtained by performing measurement based on the X-ray diffraction with respect to a plurality of test members of the coating layer heated at each of a plurality of predetermined heating temperatures for a plurality of predetermined heating times and a diffraction result obtained by performing measurement based on the X-ray diffraction with respect to a member for which contents of a tetragonal-prime phase, a tetragonal phase, and a cubic phase are known in advance to calculate the content of the tetragonal-prime phase included in each of the plurality of test members, accumulating data on a heating temperature, a heating time, and the content of the tetragonal-prime phase corresponding to each test member, and calculating a relational expression between the heating time, the heating temperature, and the content of the tetragonal-prime phase for the test member; calculating a correlation between a feature amount of a spectrum in a result obtained by measuring the plurality of test members using the Raman spectroscopy and the calculated content of the tetragonal-prime phase included in each test member; calculating, when the heating time in the heating is known with respect to the measurement member of the coating layer heated at a heating temperature of a predetermined temperature or higher, the content of the tetragonal-prime phase included in the measurement member based on the feature amount of the spectrum obtained by measuring the measurement member using the Raman spectroscopy and the correlation; and calculating the heating temperature of the measurement member based on the heating time of the measurement member, the calculated content of the tetragonal-prime phase included in the measurement member, and the relational expression.
According to a fourth aspect of the invention, in the above-described temperature estimation method, the relational expression is based on a linear relationship between a decomposition amount of the tetragonal-prime phase and ¼ powers of the heating time.
According to a fifth aspect of the invention, there is provided a content measurement method of a tetragonal-prime phase, for measuring a content of a tetragonal-prime phase included in a coating layer formed on a surface of a high temperature member, including the step of: performing Rietveld analysis with respect to each of diffraction results obtained by performing measurement based on X-ray diffraction with respect to the measurement members of the coating layer heated at a heating temperature of a predetermined temperature or higher and a diffraction result obtained by performing measurement based on the X-ray diffraction with respect to a member for which contents of a tetragonal-prime phase, a tetragonal phase, and a cubic phase are known in advance to calculate the content of the tetragonal-prime phase included in each of the plurality of measurement members.
According to a sixth aspect of the invention, there is provided a content measurement method of a tetragonal-prime phase, for measuring a content of a tetragonal-prime phase included in a coating layer formed on a surface of a high temperature member, including the steps of: performing Rietveld analysis with respect to each of diffraction results obtained by performing measurement based on the X-ray diffraction with respect to a plurality of test members of the coating layer heated at each of a plurality of predetermined heating temperatures for a plurality of predetermined heating times and a diffraction result obtained by performing measurement based on the X-ray diffraction with respect to a member for which contents of a tetragonal-prime phase, a tetragonal phase, and a cubic phase are known in advance to calculate the content of the tetragonal-prime phase included in each of the plurality of test members; calculating a correlation between a feature amount of a spectrum in a result obtained by measuring the plurality of test members using the Raman spectroscopy and the calculated content of the tetragonal-prime phase included in each test member; and calculating, when the heating time in the heating is known with respect to the measurement member of the coating layer heated at a heating temperature of a predetermined temperature or higher, the content of the tetragonal-prime phase included in the measurement member based on the feature amount of the spectrum obtained by measuring the measurement member using the Raman spectroscopy and the correlation.
According to a seventh aspect of the invention, there is provided a deterioration determination method including the steps of: calculating the content of the tetragonal-prime phase included in the measurement member by the content measurement method of the tetragonal-prime phase described above; and calculating a deterioration degree of the high temperature member based on a predetermined correspondence relationship between the content of the tetragonal-prime phase included in the measurement member and the deterioration degree of the high temperature member.
According to the above-described temperature estimation method, it is possible to estimate a surface temperature of a high temperature member.
Hereinafter, a control system according to a first embodiment of the invention will be described with reference to
A thermal barrier coating (TBC) is applied to a high temperature member exposed at a high temperature, such as a rotor-stator blade, a separation ring or a combustor of a gas turbine, by flame-spraying a flame coating material having a low thermal conductivity (for example, a ceramic-based material having a low thermal conductivity) on a surface of a heat-resistant alloy layer which is a base material in order to improve thermal insulation properties and durability. In
The flame-sprayed YSZ includes tough crystals called a T′ phase (tetragonal-prime phase) generated by being rapidly cooled, which occupy almost 100% of its content. Accordingly, almost the entirety of the YSZ when an operation of the gas turbine is started is occupied by the T′ phase. The T′ phase is relatively stabilized, but when exposed at a high temperature that exceeds 1200° C., the T′ phase is gradually decomposed into a T phase (tetragonal phase) and a C phase (cubic phase). Accordingly, during the operation time of the gas turbine, a phenomenon where the T′ phase is decomposed into the T phase and the C phase occurs, and thus, the T′ phase, the T phase, and the C phase are mixedly present in the YSZ of the top coat layer 14 formed on the surface of the high temperature member 10. Further, the T phase is stabilized at the high temperature, but when cooled at a temperature of about 600° C. or lower, the T phase is decomposed into an M phase (monoclinic phase) and a C phase. Accordingly, when the operation time of the gas turbine is terminated and the operation is stopped, the YSZ is gradually cooled, and the T phase is decomposed. Thus, the YSZ when the operation is stopped is in a state where the T′ phase, the T phase, the M phase, and the C phase are mixedly present. It is known that a cooling speed at that time affects the decomposition of the T phase into the M phase and the C phase. Since the surface temperature of the top coat layer 14 of the turbine wing 1 is also related to a cooling method or the like of the turbine wing 1, for example, the surface temperature is very useful information in design of the gas turbine, and it is important to obtain as precise a temperature as possible. For example, when the surface temperature of the TBC is estimated by the content of the T phase or M phase, since the content is affected by the cooling speed of the turbine, it may be difficult to estimate a precise temperate at a high temperature. On the other hand, if it is possible to estimate the surface temperature of the top coat layer 14 when the gas turbine is operated based on the content (residue) of the T′ phase, since the content of the T′ phase is not affected by the cooling speed of the turbine or the like, for example, it is possible to more precisely estimate the surface temperature of the TBC. In this embodiment, a method for estimating the surface temperature of the top coat layer 14 in heating based on the content of the T′ phase is provided. Hereinafter, the surface temperature of the top coat layer 14 is referred to as a TBC surface temperature.
In the Rietveld analysis, a measured XRD profile of each test piece and a theoretical XRD profile which is prepared in advance are analyzed by full pattern fitting or the like based on a non-linear least-squares method, for example, to thereby obtain a theoretical XRD profile for more precise fitting. The theoretical XRD profile is a theoretical value of diffraction result based on the X-ray diffraction generated by assuming various patterns of the contents of the T′ phase, the T phase, and the C phase and performing a simulation or the like for each pattern. As a result of the Rietveld analysis, if the theoretical XRD profile for fitting is determined, the contents of the T′ phase, the T phase, and the C phase of the test piece are determined as the contents of the T′ phase, the T phase, and the C phase assumed with respect to the determined theoretical XRD profile.
Next, a result obtained from the above experiment using an actual test piece will be described with reference to
In
f=1−αT′-YSZ=kt1/4 (1)
Further, if a linear equation that satisfies the relationship between 1/T and ln k is calculated, the following Expression (3) is obtained from
y=−8692.7x+3.9126 (3)
Further, it is possible to calculate k0=50.0 and Q=7.2×105 J/mol from a segment of ln k0=3.9126 and a slope of Q/R=−8692.7 (R is a gas constant: 8.31 J/(mol·k)). If these values are substituted in Expression (2), the following Expression (4) is obtained.
Here, when considering estimation of the TBC surface temperature of the actual machine, since the heating time (that is, a gas turbine operation time) t and the gas constant R are already known, if the content of the T′ phase (αT′-YSZ) can be obtained, the heating temperature (T) can be calculated using Expression (4). Since the heating time (T) is a temperature of a furnace when a test piece of a top coat layer is inserted into the furnace, for example, the heating temperature (T) may be considered as the TBC surface temperature in the actual machine. That is, if the content of the T′ phase included in the top coat layer 14 of the actual machine can be obtained, it is possible to obtain the TBC surface temperature using Expression (4).
The above processes correspond to processes in a preparation stage of this embodiment. That is, in the preparation stage, data in which the measured XRD profiles of the respective test pieces which are heated under the various conditions described with reference to
Next, a method for estimating a TBC surface temperature of the high temperature member 10 of an actual machine will be described with reference to
Steps S11 to S13 are processes in a preparation stage. Since these processes are the same as described above, description thereof will be briefly made. First, plural test pieces of the top coat layer 14 are prepared, and each test piece is heated at a predetermined temperature for a predetermined time to form a heated test piece (step S11). Then, measurement based on X-ray diffraction is performed with respect to each test piece, a T′ phase, a T phase, a C phase, and an M phase are identified from diffraction patterns in a diffraction result, and the content of each phase is calculated. Here, since it is difficult to identify the T′ phase, the T phase, and the C phase using the X-ray diffraction, the content of each of these phases is calculated by the Rietveld analysis using a theoretical diffraction result (theoretical XRD profile) with respect to various patterns of the contents of the T′ phase, the T phase, and the C phase (step S12). Then, the relational expression between the content of the T′ phase, the heating time, and the TBC surface temperature during heating is derived in the order described using
Then, estimation of the TBC surface temperature of the actual machine is performed. First, a TBC (top coat layer) which is a measurement target is obtained from a gas turbine after operation. Similar to step S12, X-ray diffraction and Rietveld analysis are performed with respect to the obtained measurement target TBC. In the Rietveld analysis, a target to be fitted for a measurement result based on the X-ray diffraction of the measurement target TBC may be a diffraction result based on the X-ray diffraction of the test piece analyzed in step S12 or may be a theoretical XRD profile as long as the contents of the T′ phase, the T phase and the C phase are known. Thus, the content of the T′ phase in the measurement target TBC is calculated (step S14).
Then, the content of the T′ phase calculated in step S14 and the operation time of the gas turbine are substituted in the relational expression [for example, Expression (4)] between the content of the T′ phase, the heating time, and the TBC surface temperature calculated in step S13. It is assumed that the operation time of the gas turbine is already known. The expression after substitution is solved for the TBC surface temperature (T) to calculate the TBC surface temperature (step S15). The calculated value is an estimated value of the surface temperature of the top coat layer 14 during operation of the gas turbine according to this embodiment.
According to this embodiment, it is possible to precisely calculate the content of the T′ phase in the top coat layer 14 using the X-ray diffraction and the Rietveld analysis. Further, it is possible to calculate the relational expression [for example, Expression (4)] between the content of the T′ phase, the heating time, and the TBC surface temperature from the fact that the T′ phase is decomposed into a stable T phase due to a diffusion phenomenon under a high temperature environment, the fact that a decomposition speed at that time is changed according to temperature, the fact that a reduction amount of the T′ phase at each temperature and ¼ powers of the TBC heating time is in a linear relationship (
Hereinafter, a temperature estimation method according to a second embodiment of the invention will be described with reference to
In the second embodiment, when calculating the content of a T′ phase of the TBC which is a measurement target, measurement based on Raman spectroscopy is performed. In this embodiment, first, similar to the first embodiment, X-ray diffraction and Rietveld analysis are performed with respect to test pieces having the same composition as in an actual machine, heated under various conditions, and the content of the T′ phase in each test piece is calculated. Then, the measurement based on the Raman spectroscopy is performed with respect to each test piece for which the content of the T′ phase is known. A measurement result based on the Raman spectroscopy and the content of the T′ phase are recorded in association with each other.
Next, a result obtained by performing the measurement based on the Raman spectroscopy using an actual test piece will be described with reference to
In
In
In
In this embodiment, measurement based on the Raman spectroscopy is performed with respect to test pieces for which the content of the T′ phase is known by the X-ray diffraction and the Rietveld analysis, similar to the first embodiment. Feature amounts (peak position, full width at half maximum, and peak intensity ratio) of spectrums in measurement results are extracted, and a correlation between the extracted feature amounts and the content of the T′ phase (for example,
Next, a method for estimating a TBC surface temperature of a high temperature member of an actual machine according to this embodiment will be described with reference to
Steps S11 to S13 are processes in a preparation stage. These processes are the same as in the first embodiment. That is, test pieces are heated under various conditions to form heated test pieces (step S11), and the contents of the T phase, and the like are calculated by the X-ray diffraction and the Rietveld analysis with respect to each test piece (step S12). Then, the relational expression between the content of the T′ phase, the heating time, and the TBC surface temperature during heating is derived (step S13).
In this embodiment, then, the Raman spectroscopy is performed with respect to each test piece. In consideration of a predetermined Raman peak in a measurement result obtained by the Raman spectroscopy, a correlation between each of the position of the Raman peak, a full width at half maximum of the Raman peak and an intensity ratio of the Raman peaks, and the content of the T′ phase calculated in step S12 is arranged to calculate at least one of a relational expression between the position of the Raman peak and the content of the T′ phase (for example,
Then, estimation of the TBC surface temperature of the high temperature member 10 of the actual machine is performed. First, a TBC (top coat layer) which is a measurement target is obtained from a gas turbine after operation. Measurement based on the Raman spectroscopy is performed with respect to the obtained measurement target TBC. Then, at least one of a Raman peak position, a Raman peak full width at half maximum, and a peak intensity ratio is obtained with respect to the measurement target TBC from the measurement result (step S17).
Then, the Raman peak position, the Raman peak full width at half maximum, and the peak intensity ratio calculated in step S17 are substituted in a corresponding relational expression calculated in step S16 to calculate the content of the T′ phase included in the measurement target TBC (step S18). Then, the content of the T′ phase calculated in step S18 and the operation time of the gas turbine which is already known are substituted in the relational expression [for example, Expression (4)] between the content of the T′ phase, the heating time, and the TBC surface temperature calculated in step S13. The expression after substitution is solved for the TBC surface temperature (T) to calculate the TBC surface temperature (step S15). The calculated value is an estimated value of the TBC surface temperature during heating according to this embodiment.
In the first embodiment, the Rietveld analysis is performed to calculate the content of the T′ phase included in the top coat layer 14 of the actual machine. Generally, the Rietveld analysis takes time and labor. On the other hand, in this embodiment, the content of the T′ phase included in the top coat layer 14 of the actual machine is calculated by using the Raman spectroscopy capable of being relatively easily performed by any operator, instead of the X-ray diffraction and the Rietveld analysis. Accordingly, if the preparation stage is completed, it is possible to relatively easily obtain the content of the T′ phase. Further, if the content of the T′ phase is obtained, it is possible to calculate the TBC surface temperature, similar to the first embodiment. Accordingly, according to this embodiment, it is possible to more conveniently estimate the surface temperature of the TBC regardless of an individual's skill, in addition to the effects of the first embodiment.
The Raman spectroscopy is applicable without being limited by shapes of test pieces, and a portable Raman spectroscopy device may be provided. For example, Raman spectroscopy measurement may be performed with respect to a turbine wing in a state where the device is mounted on an actual machine.
Further, the TBC surface temperature may be estimated by the following method. An estimation method of a surface temperature according to a third embodiment will be described with reference to
First, heating is performed with respect to test pieces of the top coat layer 14 under various conditions, similar to the first embodiment. Then, measurement based on the Raman spectroscopy is performed with respect to the heated test pieces. Then, a Raman spectrum obtained from the measurement is fitted by a Gaussian function and a Lorentz function to obtain a Raman peak position, a full width at half maximum, and a peak intensity. Thereafter, each of the Raman peak position, the full width at half maximum, and the intensity, a heating time, and a heating temperature are arranged using a Larson-Miller parameter (LMP=T[5+ln(t)]).
In
In
In
The relationship between the results obtained by measuring based on the Raman spectroscopy using the test pieces and the LMP value is recorded. The above processes correspond to processes in a preparation stage.
Then, a TBC surface temperature of an actual machine is estimated. First, similar to the first and second embodiments, a TBC which is a measurement target is obtained, and measurement based on the Raman spectroscopy is performed with respect to the measurement target TBC. Then, at least one of a Raman peak position, a Raman peak full width at half maximum, and a peak intensity ratio with respect to the measurement target TBC is obtained from the measurement result. Then, in a case where the Raman peak position is obtained, the LMP value of the measurement target TBC is obtained from the relationship illustrated in
T×[5+ln(t)]=LMP value obtained based on FIGS. 12 to 14 (5)
By solving Expression (5) for T, it is possible to calculate a TBC surface temperature according to the third embodiment.
However, it is known that the content of the T′ phase is in high correlation with durability against the heat cycle (R. A. Miller et al., American Ceramic Society Bulletin, 62(12), 1355, 1983). By using this characteristic and the measurement method of the content of the T′ phase according to each of the first to third embodiments, it is possible to determine deterioration of the high temperature member 10.
For example, a test piece for a heat-resistant test in which the same TBC as in an actual machine is formed on the same base material as in the actual machine is prepared, and the same thermal load as in a turbine member of the actual machine is applied to the test piece, to thereby check a deterioration degree of the test piece. For example, Japanese Patent No. 4388466 discloses a method for repeatedly applying a predetermined thermal load to a test piece and evaluating the number of times of repetition at the time when peeling of TBC occurs as a heat cycle lifetime, by a laser type heat cycle tester that heats a TBC side of the test piece using laser light and cools a base material on a rear side of the test piece (on a side opposite to the side where the TBC is provided) using a cooling gas. For example, the thermal load is repeatedly applied to the test piece for the heat-resistant test until the peeling of the TBC occurs. Here, similar to the first embodiment, for each predetermined number of times of repetition, the X-ray diffraction and the Rietveld analysis are performed with respect to the test piece to calculate the content of the T′ phase included in the TBC of the test piece. Alternatively, similar to the second embodiment, using the measurement result of the Raman spectroscopy for the TBC of the test piece and the relational expression obtained in step S16, the content of the T′ phase included in the TBC of the test piece is calculated. Further, a relationship between the number of times of repetition and the deterioration degree is defined from the number of times of repetition when the peeling of the TBC occurs (for example, if the TBC is peeled by 100 times of repetition, the deterioration degree may be set to 50% in the case of 50 times of repetition), and then, a correspondence relationship between the content of the T′ phase and the deterioration degree is recorded.
Then, a TBC which is a measurement target is obtained from the actual machine, and the content of the T′ phase of the measurement target TBC is calculated using the same method as in the first embodiment or the second embodiment. Then, it is possible to determine a deterioration degree of a turbine member of the actual machine based on the correspondence relationship between the content of the T′ phase and the deterioration degree which is prepared in advance using the test piece for the heat-resistant test.
In the first to third embodiments, an example in which the YSZ is used as the material of the top coat layer 14 is shown, but the invention is not limited thereto. In addition, stabilized zirconia (for example, YbSZ, or the like) that includes one type or two or more types of oxides (alkaline such as MgO or CaO, light rare earth such as Sc2O3 or Y2O3, or heavy rare earth such as La2O3, Ce2O3, Pr2O3, Nd2O3, Pm2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, or Lu2O3) capable of partially stabilizing zirconia (ZrO2) may be used.
In addition, the components in the above-described embodiments may be appropriately replaced with known components in a range without departing from the spirit of the invention. Further, a technical scope of the invention does not only include the above-described embodiments, but may also include various modifications in a range without departing from the spirit of the invention. In the above description, the test piece of the top coat layer 14 is an example of a test member, and the measurement target TBC is an example of a measurement member.
According to the above-described temperature estimation method, it is possible to estimate a surface temperature of a high temperature member.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2014-229619 | Nov 2014 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2015/053233 | 2/5/2015 | WO | 00 |
