Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures

Solar thermochemical water splitting: Advances in materials and methods

Photoelectrochemical (PEC) water splitting, termed artificial photosynthesis, converts solar energy into hydrogen by harvesting a narrow spectrum of visible light using photovoltaics integrated with water-splitting electrocatalysts. While conceptually attractive, critical materials issues currently challenge technology development(1) and economic viability(2). Despite decades of active research, this approach has not been demonstrated at power levels above a few watts, or for more than a few days of operation. High-temperature solar thermochemical (STCH) water splitting is an alternative approach that converts solar energy into hydrogen by using the deceptively simple metal oxide-based thermochemical cycle presented in figure 1. The STCH process requires very high temperatures, achieved by collecting and concentrating solar energy. Unlike PEC, two-step metal oxide water-splitting cycles have been demonstrated at the 100kW scale(3), and continuous operation at even higher power levels is nearing pre-commercial demonstration (HYDROSOL-3D). Nonetheless STCH, like PEC, faces critical materials issues that must be addressed for this technology to achieve commercial success. Please click Additional Files below to see the full abstract

The use of poly-cation oxides to lower the temperature of two-step thermochemical water splitting

We report the discovery of a new class of oxides - poly-cation oxides (PCOs) - that consist of multiple cations and can thermochemically split water in a two-step cycle to produce hydrogen (H-2) and oxygen (O-2). Specifically, we demonstrate H-2 yields of 10.1 +/- 0.5 mL-H-2 per g and 1.4 +/- 0.5 mL-H-2 per g from (FeMgCoNi)O-x (x approximate to 1.2) with thermal reduction temperatures of 1300 degrees C and 1100 degrees C, respectively, and also with background H-2 during the water splitting step. Remarkably, these capacities are mostly higher than those from measurements and thermodynamic analysis of state-of-the-art materials such as (substituted) ceria and spinel ferrites. Such high-performance two-step cycles 1100 degrees C are practically relevant for today's chemical infrastructure at large scale, which relies almost exclusively on thermochemical transformations in this temperature regime. It is likely that PCOs with complex cation compositions will offer new opportunities for both fundamental investigations of redox thermochemistry as well as scalable H-2 production using infrastructure-compatible chemical systems.113sciescopu