Advanced high temperature and fatigue resistant environmental barrier coating bond coat systems for SiC/SiC ceramic matrix composites
10774682 ยท 2020-09-15
Assignee
Inventors
Cpc classification
Y10T428/264
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
F01D25/005
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
C04B41/5042
CHEMISTRY; METALLURGY
C04B41/5042
CHEMISTRY; METALLURGY
International classification
F01D25/00
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
C04B41/00
CHEMISTRY; METALLURGY
C22C32/00
CHEMISTRY; METALLURGY
Abstract
Advanced environmental barrier coating bond coat systems with higher temperature capabilities and environmental resistance are disclosed. These bond coat systems can be applied to ceramic substrates such as SiC/SiC ceramic matrix composite substrates, and can provide protection from extreme temperature, mechanical loading and environmental conditions, such as in high temperature gas turbines. Example bond coat systems can include either an advanced silicon/silicide component, an oxide/silicate component, or a combination thereof.
Claims
1. An article, comprising: a substrate; and a bond coat system in contact with the substrate, wherein the bond coat system comprises a bond coat layer, and wherein the bond coat layer comprises a first component comprising a rare earth doped iron silicide and a second component comprising at least one oxide.
2. The article of claim 1, wherein the at least one oxide comprises HfO.sub.2.
3. The article of claim 1, wherein the bond coat layer comprises a layered composite comprising alternating layers of the first and second components.
4. The article of claim 1, wherein the bond coat layer comprises a mixture phased region with low oxygen activities, wherein the mixture phased region has a silicon concentration that decreases with increasing distance from the substrate.
5. The article of claim 1, wherein the bond coat system comprises a first interlayer between the bond coat layer and the substrate, and a second interlayer in contact with a face of the bond coat layer opposite the substrate.
6. The article of claim 5, wherein at least one of the first interlayer or the second interlayer comprises one of a silicon alloy, hafnium oxide, zirconium oxide, and a rare earth oxide.
7. The article of claim 1, further comprising an environmental barrier coating top coat in contact with a face of the bond coat system opposite the substrate.
8. The article of claim 7, wherein the environmental barrier top coat comprises one or more of a rare earth silicate and a rare earth aluminosilicate.
9. The article of claim 1, wherein the bond coat layer comprises one or more rare earth oxide dopants.
10. The article of claim 1, wherein the bond coat layer comprises at least 40% silicon by atomic percentage.
11. The article of claim 1, wherein the bond coat layer has a thickness less than or equal to forty micrometers.
12. The article of claim 1, wherein the bond coat layer self-grows an environmental barrier coating.
13. The article of claim 1, wherein the bond coat layer has a flexural strength of at least 100 MPa at one or more temperatures in the range from 1400 C. to 1500 C.
14. An article, comprising: a substrate; and a bond coat system in contact with the substrate, wherein the bond coat system comprises a first interlayer in contact with the substrate, a bond coat layer in contact with the first interlayer, and a second interlayer in contact with the bond coat layer, wherein the bond coat layer comprises a rare earth doped iron silicide and at least one oxide, wherein the bond coat comprises at least 40% silicon by atomic percentage.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
(12) The innovation is now described with reference to the drawings, wherein like reference numerals are used to refer to like elements throughout. In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the subject innovation. It may be evident, however, that the innovation can be practiced without these specific details. In other instances, well-known structures and devices are shown in block diagram form in order to facilitate describing the innovation.
(13) In various aspects, embodiments of the subject innovation can include systems, articles, and methods that can employ an advanced high temperature capable, low expansion and low diffusion environmental barrier coating (EBC) bond coat system for Si-based ceramics and ceramic matrix composites (CMCs). Various aspects of the subject innovation can provide coating compositions and architecture arrangements that can achieve exceptional environmental barrier coating bond coat adhesion, oxidation and fatigue resistance, and environmental protection performance, along with self-healing capabilities that can ensure log-term durability for Si-based turbine ceramic components. Environmental barrier coating bond coat systems, articles, and methods of the subject innovation can be employed in thin environmental barrier coating configurations, which can help enable the realization of ceramic turbine engine SiC/SiC CMC combustor and turbine airfoil applications.
(14) Referring initially to the drawings,
(15) EBC bond coat systems in accordance with the subject innovation can comprise one or both of two composition categories, referred to herein as Group A (also referred to herein as an silicon/silicide component) and Group B (also referred to herein as a oxide/silicate component). Group A and Group B have low oxygen activities (or called oxygen getter) and higher oxygen but lower silica activities, respectively. Members of Group A generally have superior oxidation resistance, while members of Group B generally have superior temperature resistance and combustion environmental resistance. Group A (the silicon/silicide component) can be an advanced silicon based alloy system as described herein, e.g., a rare earth (RE) based or doped silicon alloy or compound. Rare earth metals that can be employed in connection with group A include Ytterbium, Gadolinium, Neodymium, Samarium, Lutetium, Erbium, Europium, Terbium, Dysprosium, Holmium, Lanthanum, Cerium, Praseodymium, Promethium, Thulium (i.e., lanthanides), plus Yttrium and Scandium; Group A can also include doped Carbide-Nitrides of these. Group B (the oxide/silicate component) can include highly stable Oxide and Silicate based material systems described herein. Various embodiments can employ any of a variety of silicon/silicide components, or any of a variety of oxide/silicate components, or a combination of both. In some embodiments, bond coats of the subject innovation can include HfO.sub.2 (or ZrO.sub.2, etc.) and Si/alloyed/doped Si, optionally with various dopants as described herein. Various embodiments of bond coats of the subject innovation incorporating HfO.sub.2 and Si or their alloys have been demonstrated to have excellent temperature and environmental resistance, including resistance to CMAS (Calcium Magnesium Alumino-Silicate) attack.
(16) EBC bond coats in accordance with the subject innovation can have advanced multi-component compositions, which can be arranged to form thermodynamically stable, multi-scale composites that have superior performance as compared to the current state of the art silicon bond coat. Bond coat systems and articles in accordance with the subject innovation can have thermal expansion co-efficients in a range from 4-610.sup.6 m/m.Math.K, comparable to the Si-based ceramics, and conventional Silicon bond coats. Coatings of the subject innovation can be processed consistent with any of the current state-of-the-art coating processing methods.
(17) In contrast to conventional systems, embodiments of the subject innovation can comprise systems articles and methods that can utilize multi-component bond coat systems, which can include one or more of alloy doped Silicon; alloy-doped or silicon-rich Rare Earth (RE) Silicides; Rare Earth (RE) doped transition metal Silicides; Nitrogen, Boron or Carbon doped metal Silicon alloys or compounds; or advanced oxides or silicates. Embodiments of the subject innovation can form highly stable bond coat systems useable in connection with SiC/SiC CMC components.
(18) Group A (the silicon/silicide component) useable in connection with bond coat systems disclosed herein, can include (a) Rare Earth doped or alloyed Silicon, (b) Rare Earth (RE) Silicides (e.g., any of various stoichiometry compounds, such as RE.sub.5Si.sub.3, RE.sub.5Si.sub.4, RESi, RE.sub.3Si.sub.5, RESi.sub.2, etc. and also particularly non-stoichiometry silicide compound compositions disclosed herein for optimum performance enhancement), which can include Ytterbium Silicides, Yttrium Silicides, Gadolinium Silicides, Erbium Silicides, etc., (c) Rare Earth (RE) Silicides doped with Zirconium, Hafnium, Aluminum or a combination thereof, (d) Rare Earth (RE) doped refractory transition metal Silicides, which can include Rare Earth (RE) doped or alloyed Zirconium Silicides, Hafnium Silicides, Tantalum Silicides, Titanium Silicides, Chromium Silicides, Iron Silicides, Molybdenum Silicides, Niobium Silicides, Aluminum Silicides, etc., (e) Rare Earth (RE) or Aluminum doped Palladium, Irridium and Platinum Silicides; (f) Rare Earth (RE) doped or non-doped Tantalum-, Titanium-, Chromium-, Molybdenum-, Niobium-, Aluminum-Silicon Carbon, Boron, Nitride compounds with Silicon, such as Ti.sub.x(AlCrTa).sub.ySiCN, Ti.sub.x(AlCrTa).sub.ySiBN, Ti.sub.2CrTa(Si)N, ZrTaSiN, or Ta.sub.2AlSiCN, etc.; or (g) any combinations of any of the foregoing. The Group A can be doped or oxidized with minor oxygen dopant or with oxygen gradients.
(19) Group B (the oxide/silicate component) useable in connection with bond coat systems disclosed herein can significantly improve the temperature capability, environmental stability and strength capability, and can include (a) Rare Earth (RE) oxides (e.g., RE.sub.2O.sub.3), which can include Ytterbium Oxide, Yttrium Oxide, Gadolinium Oxide, Europium Oxide, etc.; (b) Rare Earth Mono-Silicates (RE.sub.2SiO.sub.5) or Di-Silicates (RE.sub.2Si.sub.2O.sub.7) such as Yb.sub.2SiO.sub.5, Yb.sub.2Si.sub.2O.sub.7, Y.sub.2SiO.sub.5, Gd.sub.2Si.sub.2O.sub.7, Gd.sub.2SiO.sub.5 and Gd.sub.2Si.sub.2O.sub.7; (c) other oxides such as Barium Oxide (BaO), Strontium Oxide (SrO), etc.; (d) Titanium and Tantalum-doped and un-doped Rare Earth Zirconium and Hafnium Pyrochlore Oxides such as RE.sub.2Zr.sub.2O.sub.7 and RE.sub.2Hf.sub.2O.sub.7; (e) Rare Earth Aluminum Garnets (REAG or Y.sub.3Al.sub.5O.sub.12, such as YAG, YbAG), Rare Earth Aluminum Monoclinics (REAM, such as YAM, YbAM) or Rare Earth Aluminum Perovskites (REAP or REAlO.sub.3, such as YAP, YbAP); (f) Zirconium Oxide (ZrO.sub.2) or Hafnium Oxide (HfO.sub.2, e.g., t Hafnium Oxide, monoclinic Hafnium Oxide, etc.), or Rare Earth (RE) Oxide Doped ZrO.sub.2 or HfO.sub.2, or Transition Metal doped, and/or SiO.sub.2 doped or alloyed ZrO.sub.2 and HfO.sub.2; or (g) any combinations of any of the foregoing. Silicates of Group B can include both rare earth rich compounds and silica (SiO.sub.2) rich compounds.
(20) Referring again to
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(24) In various embodiments of the innovation, silicon/silicide components (e.g., from Group A) can be employed that can have relatively high silicon content designs (silicon-rich, off-stoichiometry silicide compositions) to provide superior oxidation resistance. In embodiments employing doped Silicon alloys or Silicides, such high silicon content can correspond to silicon molar concentration in a range from 50 to 99.5 molar %. For embodiments employing Rare Earth Silicides and other doped Silicide embodiments, silicon-rich silicides such as RE.sub.3Si.sub.5 and RESi.sub.2 can provide such a relatively high silicon content, for example, and also RE.sub.3Si.sub.5+x and RESi.sub.2+x, where the x indicates a modified composition with the silicon rich silicides for superior performance.
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(26) Bond coats that comprise both a silicon/silicide component (e.g., from Group A) and an oxide/silicate component (e.g., from Group B) can provide for a coating with capability. The oxide/silicate component (e.g., refractory metal or rare earth oxides or silicates, etc.) can further protect the silicon/silicide component from oxidation, can improve the coating strength and toughness, creep and fatigue resistance, and can prevent the coating from Pesting in certain lower temperature conditions. The advanced RE and RE doped Silicon or Silicide of Group A and the oxide-silicate compositions of Group B can also enhance the bond coat self-healing in the event cracking develops, and can also provide excellent oxidation and combustion environment protection under extreme environments.
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(28) In various aspects of the subject innovation, environmental barrier coating bond coat systems described herein can employ any of a variety of compositions and architectures described herein. Experimental results obtained in connection with embodiments of EBC bond coat systems useable in connection with Si-based ceramic and CMC component applications have demonstrated higher temperature capabilities and durability than state-of-the-art coatings in laboratory simulated engine environments. Various aspects and embodiments of bond coating systems disclosed herein have been successfully tested and demonstrated at the sub-element and sub-component levels.
(29) In various aspects, embodiments can employ an oxide-Si bond coat as described herein, in combination with an RE silicate or RE aluminosilicate EBC. Interlayers in such an embodiment can comprise RE-HfO.sub.2 layered coatings. Various high stability coatings can be employed in various aspects of the innovation, which can include one or more of RE oxide doped HfO.sub.2/ZrO.sub.2, pyrochlores (RE.sub.2Zr.sub.2O.sub.7-RE.sub.2Zr.sub.2O.sub.7), perovskites (e.g., RE-SrZrO.sub.3, etc.), magnetoplumbites (e.g., REMgAl.sub.11O.sub.19, etc.), or RE-Hafnia plus RE aluminosilicate composite coatings.
(30) In aspects, embodiments of the subject innovation can also comprise other coats that can form an EBC system, such as top coats described herein. For example, top coats of the subject innovation can employ various materials, such as those of the form RE-HfO.sub.2X, RE-HfO.sub.2-graded Silica, RE-HfO.sub.2-Alumino Silicate, etc. Top coats can be applied via EB-PVD or other suitable techniques, such as EB-PVD HfO.sub.2-RE.sub.2O.sub.2, etc.
(31) As described above, coats and coat systems of the subject innovation can be applied via a variety of techniques, such as applied by Electron Beam-Physical Vapor Deposition (EB-PVD), Plasma-Spray Physical Vapor Deposition (PS-PVD), Plasma-Spray-Thin Film (PS-TF), High temperature Vacuum Vapor Deposition, Chemical vapor Deposition, etc. In one example, coatings comprising multicomponent RE silicate/HfO.sub.2-RE-Silicate with distinct vapor pressures can be applied via EB-PVD with co-deposition. In another example, PS-PVD and/or PS-TF coating processes can be employed, with PVD splat coating processing at low pressure (e.g., around 1 torr, etc.). For complex-shape components, high velocity vapor and non-line-of-sight coating processing can be employed. PS techniques used herein can employ a high enthalpy plasma vapor stream for efficient and complex thin film coating processing.
(32) What follows is a more detailed discussion of certain systems, methods, and apparatuses associated with aspects of the subject innovation. To aid in the understanding of aspects of the subject innovation, theoretical analysis and experimental results associated with specific experiments that were conducted are discussed herein. However, although for the purposes of obtaining the results discussed herein, specific choices were made as to the selection of various aspects of the experiments and associated setupssuch as testing temperatures, durations, and environmental conditionsthe systems and methods described herein can be employed in other contexts, as well. For example, various aspects of the subject innovation can be utilized to protect ceramic components in gas turbines or other engines, whether air-based, land-based, etc. In some embodiments, different selections of component materials for coatings can be selected than those used in the experiments discussed herein, and may have differing characteristics, as explained in greater detail below.
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(34) Several specific examples of coats and coat systems were developed as example embodiments of the innovation disclosed herein. These examples are included herein for the purposes of illustration; however, the subject innovation is not limited to these specific examples, but can include other embodiments that vary from these specific examples in one or more aspects.
(35) As a first set of specific examples, coatings in accordance with various aspects of the subject innovation can comprise (a) Silicon cladded HfO.sub.2 (e.g., agglomerated or sinter crushed HfO.sub.2 powders, which can be at or near a 30:70 weight ratio of Si:HfO.sub.2); (b) Yttrium monosilicate, with approximately a 50:50 molar ratio of Y.sub.2O.sub.3 and SiO.sub.2 (i.e., around 78.984% weight and 21.016% weight, respectively); (c) Silicon cladded ytterbium monosilicate plus minor t HfO.sub.2 (e.g., in a weight ratio of approximately 30:60:10 of Si:Ytterbium monosilicate:t HfO.sub.2); (d) Silicon cladded ytterbium monosilicate (e.g., in a weight ratio of approximately 30:70 of Si:Ytterbium monosilicate); (e) Silicon cladded t low k ZrO.sub.2 plus ytterbium silicate (e.g., with a 30:30:40 weight ratio of Si:t ZrO.sub.2:ytterbium monosilicate); (f) Yttrium silicide cladded t low k ZrO.sub.2 plus ytterbium silicate (e.g., with a 30:30:40 weight ratio of Si:t ZrO.sub.2:ytterbium monosilicate); or (g) Compound t ZrO.sub.2HfO.sub.2 (with RE) plus ytterbium silicate approximately as in table 1:
(36) TABLE-US-00001 TABLE 1 Oxide ZrO.sub.2 HfO.sub.2 Y.sub.2O.sub.3 Yb.sub.2O.sub.3 Gd.sub.2O.sub.3 Mole % Balance 20 1.5 1.5 1.5 Wt % 62.077 28.090 2.260 3.944 3.628
(37) As additional specific examples, bond coats in certain embodiments can comprise (a) Silicon with 30% atomic weight of Ytterbium; (b) alternating and co-deposition of 50% Gd.sub.2O.sub.3 with Si plus 30 at. % Yb and 50% Yb.sub.2O.sub.3 with Si plus 30 at. % Yb; or (c) a composite bond coat of HfO.sub.2 with Si plus 30 at. % Yb. The thickness of these example bond coats can be in the range of 3 to 5 mils, although greater or lesser thicknesses can be used in various embodiments. In other examples, certain embodiments of bond coat systems can comprise (a) Silicon with 15% atomic weight of Gadolinium; (b) alternating and co-deposition of 50% Gd.sub.2O.sub.3 with Si and 50% Yb.sub.2O.sub.3 with Si; or (c) a composite bond coat of HfO.sub.2 with Si plus 15 at. % Gd. As a second EBC layer, an alternating layer system can be employed with a total thickness of around 10 mils. A bottom system (of thickness around 5 mils) can be included that alternates between (a) HfO.sub.2 (5% molar, 6.086% weight), Y.sub.2O.sub.3 (5% molar, 6.529% weight), Gd.sub.2O.sub.3 (5% molar, 20.962% weight), Yb.sub.2O.sub.3 (25% molar, 45.576% weight), with co-deposition of SiO.sub.2 (60% molar, 20.847% weight) and (b) HfO.sub.2 (96% molar, 90.7333% weight), Y.sub.2O.sub.3 (2% molar, 3.464% weight), Gd.sub.2O.sub.3 (1% molar, 2.780% weight), and Yb.sub.2O.sub.3 (1% molar, 3.023% weight). A top system can be included (also of thickness around 5 mils) that alternates between (a) HfO.sub.2 (30% molar, 27.598% weight), Y.sub.2O.sub.3 (5% molar, 4.934% weight), Gd.sub.2O.sub.3 (5% molar, 7.921% weight), Yb.sub.2O.sub.3 (30% molar, 51.669% weight), with co-deposition of SiO.sub.2 (30% molar, 7.878% weight) and (b) HfO.sub.2 (96% molar, 90.7333% weight), Y.sub.2O.sub.3 (2% molar, 3.464% weight), Gd.sub.2O.sub.3 (1% molar, 2.780% weight), and Yb.sub.2O.sub.3 (1% molar, 3.023% weight). SiO.sub.2 grading can be used with both. As with other specific examples provided herein for the purposes of illustration, it is to be appreciated that the chemical compositions can vary from the specific ratios provided, while remaining within the scope of the subject innovation.
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(39) The subject innovation, in various embodiments, can provide bond coat systems that can be critical for future development of advanced high performance gas turbine engine applications. The environmental barrier bond coating system is one of the most critical technologies that can lead to the future realization of SiC/SiC CMC turbine engine combustor liners and vanes, and turbine blades, allowing the engines to be operated at much higher temperatures with significantly reduced cooling requirements. This technology can be also used in a variety of other settings in which ceramic components will be subjected to extreme temperature or environmental conditions, such as land-based stationary gas turbines for power generation, and other energy related heat engine systems.
(40) What has been described above includes examples of the innovation. It is, of course, not possible to describe every conceivable combination of components or methodologies for purposes of describing the subject innovation, but one of ordinary skill in the art may recognize that many further combinations and permutations of the innovation are possible. Accordingly, the innovation is intended to embrace all such alterations, modifications and variations that fall within the spirit and scope of the appended claims. Furthermore, to the extent that the term includes is used in either the detailed description or the claims, such term is intended to be inclusive in a manner similar to the term comprising as comprising is interpreted when employed as a transitional word in a claim.