Process for producing thermal barrier coating

Abstract

A process for producing a thermal barrier coating having an excellent thermal barrier effect and superior durability to thermal cycling. Also, a turbine member having a thermal barrier coating that has been formed using the production process, and a gas turbine. The process for producing a thermal barrier coating includes: forming a metal bonding layer (12) on a heat-resistant alloy substrate (11), and forming a ceramic layer (13) on the metal bonding layer (12) by thermal spraying of thermal spray particles having a particle size distribution in which the 10% cumulative particle size is not less than 30 μm and not more than 100 μm.

Claims

1. A process for producing a thermal barrier coating, the process comprising: forming a metal bonding layer on a heat-resistant alloy substrate; removing small size particles from material thermal spray particles using a sieve of a predetermined size mesh which can allow the small size particles to pass through, thereby obtaining thermal spray particles having a particle size distribution in which a 10% cumulative particle size is not less than 40 μm and not more than 50 μm, in which the thermal spray particles have a maximum particle size of not more than 150 μm, in which particles having a particle size of 30 μm are not more than 3% of the thermal spray particles, and in which particles having a particle size of 40 μm are not more than 8% of the thermal spray particles, and forming a ceramic layer on the metal bonding layer by thermal spraying of the thermal spray particles.

2. A process for producing a thermal barrier coating, the process comprising: forming a metal bonding layer on a heat-resistant alloy substrate for a gas turbine; removing small size particles from material thermal spray particles which are selected from the group consisting of YbSZ, YSZ, SmYbZr.sub.20.sub.7, DySZ, and ErSZ using a sieve of a predetermined size mesh which can allow the small size particles to pass through, thereby obtaining thermal spray particles having a particle size distribution in which a 10% cumulative particle size is not less than 40 μm and not more than 50 μm, in which the thermal spray particles have a maximum particle size of not more than 150 μm, in which particles having a particle size of 30 μm are not more than 3% of the thermal spray particles, and in which particles having a particle size of 40 μm are not more than 8% of the thermal spray particles; and forming a ceramic layer on the metal bonding layer by thermal spraying of the thermal spray particles.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 A schematic illustration of a cross-section of a turbine member comprising a thermal barrier coating.

(2) FIG. 2 A graph illustrating the relationship between the 10% cumulative particle size of YbSZ thermal spray particles, and the temperature difference ΔT generated inside the ceramic layer (YbSZ layer) in a thermal cycling durability test.

(3) FIG. 3 Particle size distributions of thermal spray particles.

(4) FIG. 4 An SEM photograph of a cross-section of a ceramic layer formed using thermal spray particles A.

(5) FIG. 5 An SEM photograph of a cross-section of a ceramic layer formed using thermal spray particles B.

(6) FIG. 6 An image illustrating laminar defects within the SEM photograph of FIG. 4.

(7) FIG. 7 An image illustrating laminar defects within the SEM photograph of FIG. 5.

(8) FIG. 8 A graph illustrating the thermal cycling durability of thermal barrier coatings having ceramic layers formed using thermal spray particles with different particle size distributions.

DESCRIPTION OF EMBODIMENTS

(9) An embodiment of the present invention is described below.

(10) FIG. 1 is a schematic illustration of a cross-section of a turbine member comprising a thermal barrier coating. A metal bonding layer 12 and a ceramic layer 13 are formed, in that order, as a thermal barrier coating on a heat-resistant alloy substrate 11 such as the moving blade or stationary blade of a turbine.

(11) The metal bonding layer 12 is formed from an MCrAlY alloy (wherein M represents a metal element such as Ni, Co or Fe, or a combination of two or more of these elements) or the like.

(12) Examples of the ceramic layer 13 include YbSZ (ytterbia-stabilized zirconia), YSZ (yttria-stabilized zirconia), SmYbZr.sub.2O.sub.7, DySZ (dysprosia-stabilized zirconia) and ErSZ (erbia-stabilized zirconia).

(13) The ceramic layer of the present embodiment is formed by atmospheric pressure plasma spraying. The spray particles used are formed on the metal bonding layer with a particle size distribution in which the 10% cumulative particle size is not less than 30 μm and not more than 150 μm.

(14) FIG. 2 illustrates the thermal cycling durability of thermal barrier coatings in which the ceramic layer is formed using YbSZ thermal spray particles having various values for the 10% cumulative particle size. In the figure, the horizontal axis represents the 10% cumulative particle size (d.sub.10), and the vertical axis represents the temperature difference ΔT (relative value) generated inside the ceramic layer in a thermal cycling durability test. ΔT is defined as the difference between the maximum surface heating temperature and the maximum interface temperature at which the ceramic layer can withstand in excess of 1,000 thermal cycles without being destroyed. ΔT is an indicator of the durability of the ceramic layer in the thermal cycling durability test, with a larger value of ΔT indicating a higher level of durability.

(15) To obtain the graph of FIG. 2, test pieces were prepared by using low-pressure plasma spraying to form a metal bonding layer (Ni: 32% by mass, Cr: 21% by mass, Al: 8% by mass, Y: 0.5% by mass, Co: remainder) of thickness 100 μm on a heat-resistant alloy substrate (brand name: IN-738LC) of thickness 5 mm. A thermal spray gun (F4 gun) manufactured by Sulzer Metco Ltd. was used for the thermal spraying process. The spraying conditions included a spray current of 600 (A), a spray distance of 150 (mm), a powder supply rate of 60 (g/min), an Ar/H.sub.2 ratio of 35/7.4 (1/min), and a thickness of 0.5 (mm). The thermal cycling durability was evaluated using a laser thermal cycling test disclosed in the Publication of Japanese Patent No. 4,031,631, under conditions including a heating time of 3 minutes, a cooling time of 3 minutes, a maximum interface temperature of 900° C. and various values for the maximum surface heating temperature, and the number of thermal cycles completed before detachment of the YSZ layer occurred was measured.

(16) The particle size distribution of the thermal spray particles was measured using a laser scattering/diffraction particle size distribution analyzer (manufactured by CILAS).

(17) As illustrated in FIG. 2, when the 10% cumulative particle size is 30 μm or greater, the value of ΔT is at least 600° C., and a ceramic layer having superior thermal cycling durability can be obtained. In other words, using thermal spray particles containing a minimal proportion of small particles improves the thermal cycling durability. Once the 10% cumulative particle size exceeds 60 μm, the thermal cycling durability becomes substantially constant. In consideration of the deposition efficiency, the 10% cumulative particle size for the spray particles used in the present embodiment is preferably not more than 100 μm.

(18) FIG. 3 illustrates the particle size distribution of the YbSZ thermal spray particles. In this figure, the horizontal axis represents the particle size and the vertical axis represents the frequency.

(19) The thermal spray particles A have been classified using a 44 μm sieve to remove those particles having a small particle size. The spray particles A have a maximum particle size of not more than 150 μm, and comprise not more than 1% of particles having a particle size of 30 μm, and not more than 1% of particles having a particle size of 40 μm. The 10% cumulative particle size of the spray particles A is 42 μm.

(20) The thermal spray particles B have not been classified to remove those particles having a small particle size. Although having a maximum particle size substantially similar to that of the spray particles A, the thermal spray particles B comprise 6% of particles having a particle size of 30 μm, and 10% of particles having a particle size of 40 μm. The 10% cumulative particle size of the spray particles B is 21 μm.

(21) The thermal spray particles A and the thermal spray particles B were used to form ceramic layers on test pieces. The test pieces (the materials for the heat-resistant alloy substrate and the metal bonding layer) and the thermal spray conditions used for the ceramic layer were the same as those used in acquiring the data for FIG. 2.

(22) FIG. 4 and FIG. 5 are scanning electron microscope (SEM) photographs of cross-sections of thermal barrier coatings prepared using the thermal spray particles A and the thermal spray particles B respectively. FIG. 6 and FIG. 7 are images prepared by performing image processing of the SEM photographs of FIG. 4 and FIG. 5 respectively, and illustrate fine defects (laminar defects) extending from pore origins. Measurement of the thickness of the ceramic layer within FIG. 4 and FIG. 5 revealed a thickness of 470 μm for the ceramic layer of the thermal spray particles A and a thickness of 460 μm for the ceramic layer of the thermal spray particles B.

(23) The thermal barrier coating test pieces prepared using the thermal spray particles A and the thermal spray particles B were measured for porosity of the ceramic layer, thermal conductivity, and the value of the above-mentioned ΔT as an indicator of the thermal cycling durability. The results are shown in Table 1.

(24) The porosity was determined by using an image processing method to analyze microscope photographs of a finely polished cross-section of the thermal barrier coating acquired for 5 random fields of view (observation length: approximately 3 mm) using an optical microscope (magnification: 100×). The thermal conductivity was measured using the laser flash method prescribed in JIS R 1611.

(25) TABLE-US-00001 TABLE 1 Thermal spray Thermal spray particles A particles B Porosity (%) 16 10 Thermal conductivity (kcal/mh° C.) 0.9 1 ΔT (° C.) 780 510

(26) The number of thermal cycles (relative value) endured when the above thermal barrier coating test pieces were subjected to a laser thermal cycling test under conditions including a maximum surface heating temperature of 1500° C., a maximum interface temperature of 900° C., a heating time of 3 minutes and a cooling time of 3 minutes are illustrated in FIG. 8. In this figure, the vertical axis represents the number of thermal cycles completed before destruction of the ceramic layer, reported relative to a value of 1 for the result obtained with the thermal spray particles B.

(27) Compared with the ceramic layer formed using the thermal spray particles B, the ceramic layer formed using the thermal spray particles A has increased porosity and a thermal conductivity that is approximately 10% lower. This increase in the porosity within the ceramic layer formed using the thermal spray particles A is due to the removal of the small particles and the resulting increase in the average particle size.

(28) As illustrated in FIG. 6 and FIG. 7, a plurality of laminar defects were observed in the ceramic layer formed using the thermal spray particles B. It is thought that this is due to the large proportion of fine particles within the thermal spray particles B. In contrast, in the ceramic layer formed using the thermal spray particles A, it was confirmed that because the proportion of fine particles was minimal, the occurrence of laminar defects was able to be suppressed.

(29) As illustrated in Table 1 and FIG. 8, the thermal cycling durability increased dramatically for the thermal barrier coating formed using the thermal spray particles A. This result suggests that particles having a particle size of 40 μm or less contribute to the generation of laminar defects, and also that these laminar defects have an adverse effect on the thermal cycling durability of the coating.

(30) Even when a ceramic layer of the thermal spray particles A was formed using different thermal spray conditions (such as a different spray distance), thermal cycling durability that was substantially equivalent to that illustrated in Table 1 and FIG. 8 was obtained. This result suggests that the thermal spray conditions have almost no effect on the generation of laminar defects.

(31) As described above, by using thermal spray particles in which the number of small particles (for example, particles having a particle size of 40 μm or less) has been dramatically reduced, the porosity of the ceramic layer can be increased, and a thermal barrier coating that exhibits superior thermal barrier properties and excellent thermal cycling durability can be obtained.

(32) Similarly, it has been confirmed that in the cases of YSZ and SmYbZr.sub.2O.sub.7 and the like, by forming a thermal barrier coating using thermal spray particles from which small particles have been removed in the same manner as that described above, the porosity of the ceramic layer increases and the thermal cycling durability improves.

REFERENCE SIGNS LIST

(33) 11 Heat-resistant alloy substrate 12 Metal bonding layer 13 Ceramic layer