The invention relates to a deposition technology and a deposition process for the synthesis of environmental barrier coatings (EBC) which protect Si-based Ceramic Matrix Composite (CMC) material against oxidation and volatilization at high temperatures.
Due to their high specific strength and their high temperatures stability, silicon carbide (SiC) and silicon nitride based ceramic matrix composite (CMC) materials (both summarized here under “Si-based CMC materials”) are materials of choice for the hot section in next generation gas turbine engines. However, CMCs experience rapid recession in water vapor environment resulting in the reduction of the mechanical strength and structural integrity of CMCs components. Thus, Si-based CMCs need to be protected by ceramic environmental barrier coatings (EBCs) to prevent the surface recession of these CMC materials. The approach for the coating design is based on a combination of bond coat (adhesion layer) and a chemical barrier dedicated for the specific Si-based material. For SiC-based materials, some combinations consisting of bond coat and barrier layer have been investigated in the past. Promising EBC systems consist of silicon bond coat applied to the substrate followed by rare-earth silicate protective coating layers. Among rare-earth silicates, Yb2Si2O7 appears to be the most promising candidate because of its low recession rate in water vapor containing environment, excellent phase stability up to its melting temperature of 1850° C., and reasonably well-matched coefficient of thermal expansion (CTE) with silicon based CMCs substrates.
There are different approaches to deposit such coatings onto SiC-based components utilized in the hot section of the gas turbine.
Air plasma spray process (APS) has been widely used for the dense EBCs deposition. The advantages of this technology are low cost, high deposition rate and wide composition flexibility. However, when coating the complex shaped engine parts such as blades and vanes, APS process is challenging due to the spray distance and spray angle variation which will cause non-uniform coating microstructure and thickness. In addition, the control of interfaces in APS multi-layer coatings and specific nucleation processes might be difficult due to the deposition at atmospheric conditions. Therefore, novel process approaches are needed for EBCs deposition for different engine components application which allows better control on coating microstructure and properties.
In US 2020/0039892 A1, a chemical vapor deposition (CVD) is described for the deposition of the silicon bond coat as a part of the EBC coating. This process is realized at deposition pressures in the range from about 115 torr to about 150 torr, which correspond to the range from ca 15 300 Pa to ca 20 000 Pa, and utilizes silicon-containing precursors. However, in order to dissociate the precursor and get a crystalline Si coating deposition, the required deposition temperature is above 900° C. with a preference of substrate temperatures of about 1100° C. The high deposition temperature may cause the oxidation of the SiC/SiC CMC substrate and deteriorate its mechanical properties.
In this invention, a hybrid chemical/physical vapor process was developed for the deposition of EBC coatings. A typical EBC coating consists of a layer stack shown in
The
In the following, the invention is described with reference to
The current invention uses the combination of plasma activated chemical vapor deposition (CVD) and physical vapor deposition (PVD) processes for the EBC deposition. The activation of vapor in plasma is a method which enables coating deposition at much lower temperature than in conventional CVD. This is significantly different from the conventional chemical vapor deposition such as the one used in patent application US 2020/0039892 A1.
For a better understanding between the state-of-the-art technology and the process of invention, the sequence of the process steps is explained with reference to
A Silicon bond coat, in the context of EBC layer systems, is a Si layer which exhibits excellent chemical and bonding compatibility with the CMC surface. Furthermore, the silicon bond coating should have a coefficient of thermal expansion (CTE) close to that of the CMC substrate. The silicon bond coat is typically a homogeneous layer, which may comprise alloying elements in addition to Si.
The deposition of the silicon bond coat is explained now with reference to
The pre-treatment step 104 is introduced used to clean the substrates and remove native oxide on the substrate. Plasma plays an essential role for the pre-treatment of the Si-based substrates, in addition to that plasma helps to reduce the deposition temperature. The native oxide at the surface of the Si-based substrates may prevent a good adhesion of the subsequent silicon bond coat and needs therefore to be removed. The removal of the native oxide is done by plasma activation of reactive gases utilized to reduce the oxide and form volatile compounds with oxygen which are pumped away. The creation of atomic or ionized hydrogen from a hydrogen discharge is one example for such a reactive surface pre-treatment or cleaning. Here, an argon/hydrogen discharge was used with a discharge current of 200 A, discharge voltage of 50 V, an argon flow of 60 sccm (standard cubic centimeters per minute) and a hydrogen flow of 300 sccm. Also loose carbon contaminations are volatilized in such a process. Typical thickness of these oxides or carbon contaminations are in the order of 10 nm.
An exposure of as cleaned substrate surfaces to ambient would result in an immediate recontamination of the as treated substrate surface because such a pre-treated surface is high susceptible to reactions with gases in ambient atmosphere, as it is known by persons skilled in vacuum deposition technology. Therefore, there must be the direct transition without vacuum break to the next process step for the deposition of the EBC, the silicon bond coat. All this, surface pre-treatment, cleaning and controlled vacuum environment ensure a better control for the nucleation processes of the silicon bond coat on the Si-based substrate and therefore a better formation of the interface.
The formation of the interface is illustrated in
In the context of the present innovation, vacuum is understood as pressure less than 1×103 Pa but not lower than 1×10−6 Pa. The pressure range between 100 Pa and 0.001 Pa is most preferred. Pressure above 1×103 Pa increases risk for contamination, while pressure below 1×10−6 Pa cross over to the ultra-high vacuum range where special material and equipment, such as vacuum pumps is required.
The cross section micrograph obtained by TEM of the silicon bond coat deposited on SiC substrate demonstrates that columnar growth can be achieved and that the inventive plasma processing is an appropriate technique to control the nucleation and growth of the silicon bond coat at low temperature.
The excellent adhesion of the silicon bond coat to the substrate is characterized by the formation of dislocations in the substrate surface. This is illustrated in
Another feature of the inventive process is the utilization of an arc discharge for the dissociation of the gas precursor, in this example silane. The high electron current density of the arc discharge, typical parameter of such a discharge are 20 A to 1000 A at voltages between 15 V and 100 V, result in a complete dissociation of the precursor. This means that approximately 100% of the Si fed into the system with the precursor will undergo reaction in the chamber. This is different from other types of plasma enhanced CVD processes in which some amount of unreacted Si-containing (silicon containing) precursors are pumped away. The complete dissociation also produces silicon coatings which are free from hydrogen or show only very little hydrogen content in the as deposited silicon bond coat. This contributes strongly to the stability of the silicon bond coat at high temperatures, because hydrogen contribute to destabilization. The hydrogen content in the silicon bond coat was measured by Elastic Recoil Detection and is below 5 at. %, usually even below 3 at. %. Important is that these characteristics of the inventive process are realized at moderate and low substrate temperatures below 600° C.
The deposition of the Si bond coat is realized by plasma activation and dissociation of silicon containing precursors. A variety silicon containing gases can be used as Si-containing precursor and may comprise one or more of the following chemicals: Silane, Disilane, Dichlorosilane, Trichlorosilane, Silicon Tetrachloride, Methylsilane, Silicon Tetrafluoride, Trimethysilane, Tetramethylsilane, Hexachlorodisilane etc. The typical flow rate for the Silicon containing precursor gas ranges from 1 sccm to 10 l/m, preferably between 10 sccm to 1 l/m. In the following experiments, silane is used as a precursor. For the activation of the precursor, an arc discharge is utilized. This arc discharge is characterized by electron currents between 10 A and 400 A and discharge voltages between 15 V and 100 V. The arc discharge can be created by the discharge in a noble gas, like argon, or by cathodic arc evaporation of a metallic target. The high electron current of the arc discharge is very efficient for the dissociation of the silicon containing precursor. This is the precondition to synthesize silicon coatings with high deposition rates at substrate temperatures below 600° C. The degree of utilization of the silicon in the precursor is determined as the ratio of silicon atoms deposited in the chamber and the silicon atoms fed to the chamber by the precursor. The degree of utilization according to the inventive process is above 80%, preferably above 90%. Due to the very efficient dissociation of the silicon containing precursor enhanced by the argon plasma gas, the coating deposition rate shows nearly no dependency from substrate temperature in the range between 300° C. and 600° C. This is an advantage over conventional thermal CVD technology in which the substrate temperature has dominant influence on deposition rate.
Another advantage of the inventive process is the possibility to combine the plasma activated deposition with additional doping sources. As an example, for doping of the silicon bond with another element, the process technology allows to run the silicon containing precursor with an additional gaseous precursor, for example a carbon- or boron-containing precursor or combination of these. Additionally the inventive process allows also the simultaneous evaporation from silicon containing precursor in combination with a solid state source. The solid state source can particularly be the volatilization of a metal or semimetal by cathodic arc evaporation or sputtering. As an example, utilizing the process parameter mentioned above for the silicon bond coat deposition, an additional sputter source with an aluminum target can be initiated resulting in doping of the silicon bond coat by aluminum. Also other targets for sputtering or cathodic arc evaporation can be utilized for doping the silicon bond coat with suitable elements. Chemicals comprising of one or more of the following elements can be incorporated in the silicon bond coat: Al, B, C, O, N, Ga, In, P, Li, Na, K, Ca, Mg, Sr, Ba.
In
In addition to substrate pre-treatment and deposition of silicon bond coat, the inventive process includes also the synthesis of complete EBC layer stacks. In the inventive process, also this complete process sequence is realized in one process, i.e. without vacuum interruption. This is illustrated in the process sequence shown in
In an EBC coating system, the barrier coating serves as a chemical barrier between the silicon bond coating and a barrier coating or a top layer. The barrier coating should avoid potential chemical reactions that would damage the EBC. The barrier coating should protect the bond coating from oxidation and should ideally be resistant against water vapor attacks.
Another example of a coating system produced by the inventive process is given in
Another example for the current invention is shown in
In one further aspect of the invention, the coating method can be used to produce barrier coatings which comprise one or more Yb—Si—O phases combined with at least one second type of phase that does not contain Yb. The combination of Yb—Si—O with second type of phases allows the tailoring of the coefficient of thermal expansion for different substrates and coating layers. The second type of phase may be Al2O3, an alkali metal oxide or an alkaline earth metal oxide. In particular, Yb2Si2O7 or Yb2SiO5 can be combined with Al2O3, an alkali metal oxide or an alkaline earth metal oxide. The presented EBC layer stacks demonstrate the ability of the invented process for the fabrication of such a structure in one process sequence.
The
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/000107 | 11/30/2022 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 63284243 | Nov 2021 | US |