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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2006

Thermal Expansion and Thermal Conductivity of Rare Earth Silicates

Rare earth silicates are considered promising candidate materials for environmental barrier coatings applications at elevated temperature for ceramic matrix composites. High temperature thermophysical properties are of great importance for coating system design and development. In this study, the thermal expansion and thermal conductivity of hot-pressed rare earth silicate materials were characterized at temperatures up to 1400 C. The effects of specimen porosity, composition and microstructure on the properties were also investigated. The materials processing and testing issues affecting the measurements will also be discussed.

Zhu, Dongming↗
NASA NTRS2015

Thermochemistry of Rare Earth Silicates for Environmental Barrier Coatings

Rare earth silicates are promising candidates as environmental protective coatings (EBCs) for silica-forming ceramics and composites in combustion environments since they are predicted to have lower reactivity with the water vapor combustion products. The reactivity of rare earth silicates is assessed by the thermodynamic activity of the silica component which is best measured by Knudsen effusion mass spectrometry (KEMS). Here, we discuss a novel method based on a reducing agent to increase the partial pressure of SiO(g) which is then used to calculate thermodynamic activity of silica in Y2O3-SiO2 and Yb2O3-SiO2 systems. After the KEMS measurements, samples were probed by X-ray diffraction and their phase content was calculated from Rietveld refinement.

Rare Earth Silicates↗
DOE OSTI2025

Melting temperature, emissivity, and thermal conductivity of rare-earth silicates for thermal and environmental barrier coatings

In recent years, rare-earth silicates have become the industry standard for coating state-of-the-art SiC ceramic matrix composite (CMC) gas turbine engine components, due to their low volatility, high melting point, and thermal shock resistance. Current research is focused on designing rare-earth silicate based thermal-environmental barrier coatings (T/EBCs) with improved resistance to CMAS (CaO-MgO-Al 2 O 3 -SiO 2 ), steam, and crack formation, while maintaining high temperature performance and stability. Here, in this work we compare the high temperature performance of a variety of single and multi-component rare-earth mono- and disilicates (MS, DS) and rare earth apatites by measuring their melting points and spectrally averaged visible emissivities using laser heating and radiation pyrometry. We also report room temperature thermal conductivity measured by time-domain thermoreflectance (TDTR).

Environmental barrier coatings↗
DOE OSTI2022

Structure and thermodynamics of calcium rare earth silicate oxyapatites, Ca 2 RE 8 (SiO 4 ) 6 O 2 (RE = Pr, Tb, Ho, Tm)

Calcium rare earth silicate oxyapatites, (Ca 2 RE 8 (SiO 4 ) 6 O 2 ), are of interest as components of glass-ceramic nuclear waste forms. To assess their long-term behavior in a geologic repository, it is essential to determine their structure and thermodynamic stability at relevant conditions. Here, in this work, we performed detailed structural and thermodynamic investigations on Ca 2 Pr 8 (SiO 4 ) 6 O 2 , Ca 2 Tb 8 (SiO 4 ) 6 O 2 , Ca 2 Ho 8 (SiO 4 ) 6 O 2 , and Ca 2 Tm 8 (SiO 4 ) 6 O 2 by high energy synchrotron powder X-ray diffraction combined with Rietveld analysis and high temperature oxide melt drop solution calorimetry. Enthalpies of formation from constituent oxides (ΔH f,ox ) were determined to be -765.1 ± 22.8 kJ/mol for Ca 2 Pr 8 (SiO 4 ) 6 O 2 ; -638.9 ± 20.5 kJ/mol for Ca 2 Tb 8 (SiO 4 ) 6 O 2 ; -643.3 ± 10.3 kJ/mol for Ca 2 Ho 8 (SiO 4 ) 6 O 2 ; and -403.2 ± 5.1 kJ/mol for Ca 2 Tm 8 (SiO 4 ) 6 O 2 . These thermodynamic parameters were used in assessing the thermochemical stability of these phases in the presence of water vapor from room temperature to 600 K, as encountered in the subsurface environments of a geological repository.

36 MATERIALS SCIENCE↗
NASA NTRS2021

Thermodynamics of the Lu2O3 – SiO2 system and comparison to other Rare Earth Silicates

Environmental barrier coatings are necessary to protect SiC based ceramics and composites from water vapor degradation in harsh engine environments. Currently, rare earth (RE) silicates are the most promising systems to protect SiC based ceramics and composites. This protection is largely based on reduced silica activity in these rare earth silicates which results in a lowered reactivity with water vapor. To that end, previous Knudsen effusion mass spectrometry (KEMS) studies have explored RE = Yb, Y silicates to measure the reduced silica activity and subsequent water vapor reactivity. Similarly, this work employs the KEMS technique to measure the SiO(g) vapor pressure in Lu containing RE silicates to calculate the activity of silica within the monosilicate [log(a(SiO2)) = -2351.1*1/T-1.6731] and the disilicate (log(a(SiO2)) = -4884.0*1/T + 2.2208) as a function of temperature. The enthalpies of formation for Lu monosilicate from the oxides and the elements were calculated to be -45±3 kJ/mol at 1550 K and -2831.1±12 kJ/mol at 298 K, respectively. The measured enthalpy of formation and those found in literature are compared to modeled values from density functional theory and those estimated using electronegativity.

Knudesen Effusion Mass Spectrometry↗
NASA NTRSDate not supplied

Machine Learning Approaches for Rare-Earth Silicate Environmental Barrier Coating Thermochemical and Thermomechanical Property Predictions

Environmental barrier coatings (EBCs) are a necessary enabling technology for the transition from superalloys to silicon carbide (SiC) ceramic matrix composites (CMCs) in gas turbine engines for increased efficiency and decreased fuel costs. SiC-based CMCs are prone to oxidation-based degradation in the engine hot section, and rare-earth (RE) silicates are promising candidates for EBCs due to their close thermal expansion match to the composite substrate and oxidation resistance. However, the design of EBCs is hindered by the large chemical space of candidate materials and the difficulty in obtaining material properties for engineering optimization. This is especially difficult as research continues into mixed-cation or “high-entropy” RE silicates. First-principles computational methods such as density functional theory (DFT) are highly effective at calculating material properties to guide coating design but are limited by their computational cost. Atomistic simulations have the potential to both accelerate property calculations and expand the properties able to be calculated due to their lower computational compared to DFT. However, they require interatomic potentials (IAPs) specific to the material system of interest, and, to our knowledge, there are no suitable IAPs for RE silicates. Machine learning (ML) is a promising technique to accelerate material property predictions indirectly by generating IAPs for atomistic simulations or via direct prediction. In this work, we present two ML approaches to accelerate the calculation of RE silicate properties relevant to EBC design: 1) a ML-derived interatomic potential (IAP) for atomistic simulations of yttrium disilicate (Y2Si2O7) from DFT training data, and 2) a neural network (NN) model to directly predict thermochemical properties of RE silicates and oxides directly from easily obtainable unit cell parameters. Classical MD simulations using the IAP yield lattice properties and bond lengths in good agreement with both DFT and experimental results from x-ray diffraction. Thermodynamic properties calculated using the finite-displacement phonon method and quasi-harmonic approximation were orders of magnitude faster than DFT with good agreement to the DFT results. The IAP was also used to calculate properties such as coefficient of thermal expansion (CTE) that require large simulation supercells and are therefore difficult with DFT. The IAP correctly predicted the anisotropic nature of the CTE in three different phases of Y2Si2O7. The NN model predicts constant pressure heat capacity, Cp, orders of magnitude faster than DFT calculations, which can enable its use as a surrogate model for multiscale simulations. The two methods presented in this work demonstrate the utility of ML for accelerating the prediction of RE silicate properties, which can in turn accelerate EBC design and optimization.

machine learning↗
DOE OSTI2022

Steam oxidation and microstructural evolution of rare earth silicate environmental barrier coatings

A primary failure mode for environmental barrier coatings (EBCs) on SiC ceramic matrix composites (CMCs) is the oxidation of the intermediate Si-bond coating, where the formation of SiO 2 at the bond coating–EBC interface results in debonding and spallation. This work compares the microstructure evolution and steam oxidation kinetics of the Si-bond coating beneath yttrium/ytterbium disilicate ((Y/Yb)DS) and ytterbium disilicate/monosilicate (YbDS/YbMS) EBCs to better understand the impact of EBC composition on oxidation kinetics. After 500 1-h cycles at 1350°C, (Y/Yb)DS displayed a decreasing concentration of the monosilicate minor phase and increasing concentration of porosity as furnace cycling time increased, whereas the YbDS/YbMS EBC displayed negligible microstructural evolution. For both EBC systems, thermally grown oxide growth rates in steam were found to increase by approximately an order magnitude compared to dry air oxidation. The (Y/Yb)DS EBC displayed a reduced steam oxidation rate compared to YbDS/YbMS.

36 MATERIALS SCIENCE↗
NASA NTRS2023

Estimates of Permeability of Water in Rare Earth Silicates Using the Modified Theory of Deal and Grove

The salient elements of the theory of oxide growth under an environmental barrier are reviewed. In addition, the results from steam oxidation tests recently conducted on environmental barrier coated specimens are reported. The oxide thickness between the coating and substrate are reported as a function of time. Also, the results from previously conducted steam oxidation tests are reviewed. An approach to estimate the permeability of water through the various coating systems using the oxide thickness versus time measurements and the theory of oxide growth is demonstrated. Although the steam oxidation tests may have been performed under disparate conditions, the approach allows one to rank the protection efficiency of the various coating systems against substrate oxidation on an equivalent basis.

environmental barrier coatings↗
NASA NTRS2004

Multilayer article having stabilized zirconia outer layer and chemical barrier layer

A multilayer article includes a substrate that includes at least one of a ceramic compound and a Si-containing metal alloy. An outer layer includes stabilized zirconia. Intermediate layers are located between the outer layer and the substrate and include a mullite-containing layer and a chemical barrier layer. The mullite-containing layer includes 1) mullite or 2) mullite and an alkaline earth metal aluminosilicate. The chemical barrier layer is located between the mullite-containing layer and the outer layer. The chemical barrier layer includes at least one of mullite, hafnia, hafnium silicate and rare earth silicate (e.g., at least one of RE.sub.2 SiO.sub.5 and RE.sub.2 Si.sub.2 O.sub.7 where RE is Sc or Yb). The multilayer article is characterized by the combination of the chemical barrier layer and by its lack of a layer consisting essentially of barium strontium aluminosilicate between the mullite-containing layer and the chemical barrier layer. Such a barium strontium aluminosilicate layer may undesirably lead to the formation of a low melting glass or unnecessarily increase the layer thickness with concomitant reduced durability of the multilayer article. In particular, the chemical barrier layer may include at least one of hafnia, hafnium silicate and rare earth silicate.

Lee, Kang N.↗
NASA NTRS2019

Thermochemistry of Protective Coatings and Molten Silicate Debris

The durability of gas-turbine engine components can be significantly affected by the ingestion of siliceous particles, which can melt at high temperature and corrode protective coatings that are essential for long life requirements. The silicate debris consists mainly of CaO-MgO-Al2O3-SiO2 (CMAS) and is usually ingested by aircraft engines during and after take-off, sticking to their hot surfaces and resulting in the formation of calcium rare-earth silicate oxyapatites. The thermochemistry of coatings and their reaction products with molten silicate debris are crucial to understand in order to improve the durability of gas-turbine engines. Here we discuss results of high temperature drop solution calorimetry, drop-and-catch calorimetry (DnC) and differential thermal analysis (DTA) techniques for the thermodynamic properties of both thermal barrier coatings (TBCs) and environmental barrier coatings (EBCs) and their reaction with CMAS compositions. The enthalpies of solution of Y2Si2O7, Yb2Si2O7, 31YSZ, and 16RESZ based coatings and the oxyapatite are moderately positive. However, oxyapatite formation is only favorable over coating dissolution in terms of enthalpy for 7YSZ. The enthalpies of mixing between the coatings and the molten silicate are less exothermic for Yb2Si2O7 and CaYb4Si3O13 than for 7YSZ, indicating lower energetic stability of the latter against molten silicate corrosion. We also report for the first time the calorimetric measurements of the enthalpies of formation of rare-earth silicate based EBC coatings and oxyapatites (rare-earth, RE = Y, Yb, Gd, Dy, Er, Nd and Sm).

Costa, Gustavo↗
DOE OSTI2021

Synthesis and Single Crystals of Refractory Oxides of Lanthanides and Thorium

At the completion of this program, we can report that we developed a considerable degree of technical improvements in our ability to perform hydrothermal reactions at high temperatures and pressures. We can now routinely perform reactions at 700-750°C and 200 MPa. Currently we are in the process of exploiting this new technology synthesizing a range of exotic new materials investigating relatively poorly understood materials. Our initial efforts focused on the chemistry of rare earth oxides with tetravalent and pentavalent oxides. We recently published a study of the lanthanides with Nb 5+ and Ta 5+ ions, where we grew oxides such as RENdO 4 and RETaO 4 as high quality single crystals. These compounds were targeted as potential hosts for luminescent and scintillation materials, particularly given that they are among the densest oxide hosts and hence have good potential as absorbers for high energy radiation like X-rays and gamma rays. We also isolated a range of unusual new rare earth tantalates with very complex structures. indicating that the chemistry is very sensitive to conditions. We performed some fairly comprehensive examinations of the solid-state chemistry of rare earth ions with various tetravalent metal ions especially Si 4+ , Ge 4+ , Sn 4+ and Ti 4+ . Given the potential role of rare earth silicates in immobilizing radioactive waste elements in long-term storage, and the similarity of our hydrothermal fluids with known geological conditions, this chemistry continues to be relevant. We prepared an extensive series of new lanthanide germanates (e.g. RE 13 Ge 6 O 31 (OH), BaRE 10 (GeO 4 ) 4 O 8 ). and found that there is there is almost no overlap between the chemistry of the rare earth silicates. Stannic oxide (SnO 2 ) is much more refractory and requires higher temperatures and of mineralizer concentrations. One significant result is the growth of RE 2 Sn 2 O 7 pyrochlore single crystals. These are of interest because the rare earth stannate pyrochlores are known to display a wide range of magnetic frustration such as spin ice behavior. We grew high quality single crystals of rare earth germanate and stannate pyrochlores and this led to a collaboration with Professor Kate Ross at Colorado State. Preliminary measurements, indicate that the crystals contain no detectable defects or site disorder. Initial neutron diffraction on single crystals was performed at Oak Ridge, and more detailed experiments involving the Ross group are underway at both NIST and ORNL. This particular chemistry has turned out to be the most potentially significant work on this project and the collaborative effort with Prof. Ross is the topic of a DoE renewal project on quantum materials. Our initial foray into the hydrothermal chemistry of rare earth titanates has also been very promising and a range of cubic and polar ferroic phases of the light rare earths RE 2 Ti 2 O 7 (RE = La - Pr) in the P2 1 phase. We also discovered an interesting new phase Ce 2 Ti 4 O 11 that can have implications in heavy metal immobilization and storage. along with a series of new rare earth titanates (La 5 Ti 4 O 15 (OH) Sm 3 TiO 5 (OH) 3 and Lu 5 Ti 2 O 11 (OH) with exceptionally complex structures. One interesting sidelight has been high temperature hydrothermal chemistry terbium, including the growth of large crystals of TbO(OH). This is not a new compound but it is the first time it has been grown as large single crystals. The Tb atom density is almost as high as that in Tb 2 O 3 and has a very high Verdet constant (ca. 70), making it a very attractive candidate as a Faraday rotator. Unfortunately it is not in a cubic structure but he material is hard, stable, pure and inexpensive, so should still be an attractive Faraday oscillator. We recently received a patent on this material. We also synthesized K 2 Tb(Ge 2 O 7 ) containing stable octahedral Tb 4+ ions, which appears to be the first example of a well-characterized Tb 4+ complex. Given that Tb 4+ has been proposed as a benign surrogate for more treacherous tetravalent ions such as Cf 4+ and Bk 4+ , we think that Tb 4+ silicates can be a particularly useful study for actinide immobilization and related work. We also began reaction studies with rare earths and both ReO 2 and RuO 2 . These resulted in large single crystals of species like RE 5 Ru 2 O 12 , RE 4 Re 2 O 11 , REReO 4 and RE 2 ReO 5 . Several of these samples have already been sent to ORNL for magnetic and neutron diffraction studies.

36 MATERIALS SCIENCE↗
NASA NTRS2016

Microstructure Evolution and Durability of Advanced Environmental Barrier Coating Systems for SiC/SiC Ceramic Matrix Composites

Environmental barrier coated SiC-SiC ceramic matrix composites (CMCs) systems will play a crucial role in next generation turbine engines for hot-section component applications because of their ability to significantly increase engine operating temperatures with improved efficiency, reduce engine weight and cooling requirements. Advanced HfO2 and rare earth silicate environmental barrier coatings (EBCs), along with multicomponent hafnium and rare earth silicide EBC bond coats have been developed. The coating degradation mechanisms in the laboratory simulated engine thermal cycling, and fatigue-creep operating environments are also being investigated. This paper will focus on the microstructural and compositional evolutions of an advanced environmental barrier coating system on a SiC-SiC CMC substrate during the high temperature simulated durability tests, by using a Field Emission Gun Scanning Electron Microscopy, Energy Dispersive Spectroscopy (EDS) and Wavelength Dispersive Spectroscopy (WDS). The effects of Calcium-Magnesium-Alumino-Silicate (CMAS) from road sand or volcano-ash deposits on the degradation mechanisms of the environmental barrier coating systems will also be discussed. The detailed analysis results help understand the EBC-CMC system performance, aiming at the durability improvements to achieve more robust, prime-reliant environmental barrier coatings.

ceramic matrix composites↗
NASA NTRS2004

Durability of Environmental Barrier Coatings in a Water Vapor/Oxygen Environment

Silicon carbide (Sic) and silicon nitride (Si3N4) show potential for application in the hot sections of advanced jet engines. The oxidation behavior of these materials has been studied in great detail. In a pure oxygen environment, a silica (SiO2) layer forms on the surface and provides protection from further oxidation. Initial oxidation is rapid, but slows as silica layer grows; this is known as parabolic oxidation. When exposed to model fuel-lean combustion applications (standard in jet engines), wherein the partial pressure of water vapor is approximately 0.5 atm., these materials exhibit different characteristics. In such an environment, the primary oxidant to form silica is water vapor. At the same time, water vapor reacts with the surface oxide to form gaseous silicon hydroxide (Si(OH)4). The simultaneous formation of both silica and Si(OH)4 -the latter which is lost to the atmosphere- the material continues to recede. Recession rates for uncoated Sic and Si3N4 are unacceptably high, for use in jet engines, - on the order of 1mm/4000h. External coatings have been developed that protect Si-based materials from water vapor attack. One such coating consists of a Ba(0.75)Sr(0.25)Al2Si2O8 (BSAS) topcoat, a mullite/BSAS intermediate layer and a Si bond coat. The key function of the topcoat is to protect the Si-base material from water vapor; therefore it must be fairly stable in water vapor (recession rate of about 1mm/40,000h) and remain crack free. Although BSAS is much more resistant to water vapor attack than pure silica, it exhibits a linear weight loss in 50% H2O - 50% O2 at 1500 C. The objective of my research is to determine the oxidation behavior of a number of alternate hot-pressed monolithic top coat candidates. Potential coatings were exposed at 1500 C to a 50% H2O - 50% O2 gas mixture flowing at 4.4 cm/s . These included rare- earth silicates, barium-strontium aluminosilicates. When weight changes were measured with a continuously recording microbalance, linear weight loss was observed. BSAS materials have a fairly high volatility at this temperature, but rare-earth mono-silicate compounds were significantly more stable.

Holchin, John E.↗
NASA NTRS2002

Additive Effects on Si3n4 Oxidation/Volatilization in Water Vapor

Two commercially available additive-containing silicon nitride materials were exposed in four environments which range in severity from dry oxygen at 1 atm pressure, and low gas velocity to an actual turbine engine. Oxidation and volatilization kinetics were monitored at temperatures ranging from 1066 to 1400 C. The main purpose of this paper is to examine the surface oxide morphology resulting from the exposures. It was found that the material surface was enriched in rare earth silicate phases in combustion environments when compared to the oxides formed on materials exposed in dry oxygen. However, the in situ formation of rare earth disilicate phases offered little additional protection from the volatilization of silica observed in combustion environments. It was concluded that externally applied environmental barrier coatings are needed to protect additive-containing silicon nitride materials from volatilization reactions in combustion environments. Introduction Si3N4 is proposed for use as components, such as vanes, in turbine applications. Tens of thousands of hours of life are needed for both land-based turbines and aeropropulsion applications. Additive-containing SisN4 materials are

Opila, Elizabeth J.↗
NASA NTRS2020

Calorimetric Measurements of the Thermodynamic Properties of RE-Silicate Coating Materials

Thermodynamic quantities of coatings materials and siliceous debris-induced corrosion products are crucial to understand in order to develop mitigation strategies necessary to improve the durability of gas-turbine engines. Siliceous induced corrosion can occur when debris consisting mainly of CaO-MgO-Al2O3-SiO2 (CMAS) is ingested by aircraft engines during and after take-off, which sticks to hot surfaces and forms calcium rare-earth silicate oxyapatites. In this work, high-temperature oxide melt drop solution calorimetry (HT drop solution calorimetry) was used to obtain the enthalpies of formation for RE silicate (RE2Si2O7, RE2SiO5 where RE = Yb, Er, Y, Dy, Nd, Lu and Gd) environmental barrier coatings (EBCs) and the calcium RE silicate oxyapatite Ca2RE8(SiO4)6O2 (RE = Yb, Er, Y, Dy, Nd, Gd and Sm) corrosion products. Trends in the enthalpy of formation as a function of the ionic potential of the rare-earth cations in their related crystallographic sites are discussed.

Costa, Gustavo↗
NASA NTRS2016

Combined Thermomechanical and Environmental Durability of Environmental Barrier Coating Systems on SiC/SiC Ceramic Matrix Composites

Environmental barrier coatings (EBCs) and SiC/SiC ceramic matrix composites (CMCs) will play a crucial role in next generation turbine engines for hot-section component applications. The development of prime-reliant environmental barrier coatings is essential to the EBC-CMC system durability, ensuring the successful implementations of the high temperature and lightweight engine component technologies for engine applications.This paper will emphasize recent NASA environmental barrier coating and CMC developments for SiC/SiC turbine airfoil components, utilizing advanced coating compositions and processing methods. The emphasis has been particularly placed on thermomechanical and environment durability evaluations of EBC-CMC systems. We have also addressed the integration of the EBCs with advanced SiC/SiC CMCs, and studied the effects of combustion environments and Calcium-Magnesium-Alumino-Silicate (CMAS) deposits on the durability of the EBC-CMC systems under thermal gradient and mechanical loading conditions. Advanced environmental barrier coating systems, including multicomponent rare earth silicate EBCs and HfO2-Si based bond coats, will be discussed for the performance improvements to achieve better temperature capability and CMAS resistance for future engine operating conditions.

Ceramic Matrix Composites↗
DOE OSTI2024

Review of allanite: Properties, occurrence and mineral processing technologies

Allanite is commonly encountered as an accessory rare-earth silicate mineral in association with minerals such as garnet, biotite, and feldspar. It is distributed globally and occurs in igneous formations such as granites, pegmatites, and syenites, as well as in various metamorphic rocks such as schist, gneiss, and amphibolite. Moreover, it can be found in mineral veins formed through hydrothermal activity. While allanite has not yet been extensively utilized for the production of rare-earth elements, recent discoveries of high-grade rare-earth-rich allanite deposits in Wyoming, USA, highlight its economic potential. However, despite ongoing research on the mineralogy and processing of rare-earth minerals, allanite has not received widespread attention in mineral processing. To achieve economical extraction of rare-earth elements from allanite in the future, systematic studies on processing techniques (e.g., density separation, magnetic separation, flotation, leaching) are imperative to fully unlock the potential of allanite as a rare-earth element source. To pave the way for future investigation of allanite and address the unique processing challenges, this review article aims to comprehensively summarize previous studies, encompassing properties, occurrences, and processing technologies of allanite.

42 ENGINEERING↗