Two-step thermochemical solar-to-fuel efficiency computation of strontium and chromium doped lanthanum manganite perovskite oxides using CALPHAD

Reducing greenhouse gas emissions and profiting on novel synthetic fuels to store and buffer energy from renewable sources (such as solar or wind) is a prime strategy to encounter the global energy challenge. Here, two-step thermochemical fuel production is an energy technology utilizing intermittent solar power to convert water and carbon dioxide into syngas, a renewable fuel that can be stored easily and mitigate CO2 emissions. Success of the technology relies on the discovery of materials with a high thermochemical solar-to-fuel efficiency. Perovskites have attracted much attention recently due to impressive fuel productivity[1, 2]. Although a high fuel productivity shows the feasibility of a material, it does not imply that it is the optimum and most efficient material as it depends largely on the operation of the solar-to-fuel reactor [3, 4]. Literature on thermochemical solar-to-fuel efficiency of perovskites is limited and none of the existing studies measures the thermodynamic properties in the entire temperature range relevant for solar-to-fuel production, namely 1000-1800K. In this work, we use oxygen nonstoichiometry from CALPHAD data libraries on A-site doped La1-xSrxMnO3-δ and B-site doped perovskite La0.6Sr0.4Mn1-yCryO3-δ in a relevant temperature range of 1073-1873K to determine the solar thermochemical efficiency. The oxygen nonstoichiometry and thermodynamic properties extracted from CALPHAD libraries are compared to earlier studies of La1-xSrxMnO3-δ for thermochemical fuel production. We discuss diffferences between the earlier extrapolated models and the CALPHAD descriptions on the presented material examples. Specifically, we show thermochemical equilibrium models of fuel productivity supplemented by validations with experimental results on La1-xSrxMnO3-δ in literature. We make predictions on the most efficient material in the composition space La1-xSrxMn1-yCryO3-δ for different conditions. It is shown that the amount of experimental work can be reduced substantially by using the CALPHAD approach and further making predictions for multi-component systems that would be practically unattainable without this method. The solar-to-fuel field will benefit directly from additional thermodynamic data on perovskites in the relevant temperature range. Further, we provide guidelines in terms of key CALPHAD experiments that enables a mapping of the thermodynamic properties of a wide compositional space of perovskites to find materials with a high thermochemical efficiency. 1. McDaniel, A.H., et al., Sr-and Mn-doped LaAlO3−δ for solar thermochemical H2 and CO production. Energy & Environmental Science, 2013. 6(8): p. 2424-2428. 2. Bork, A.H., et al., Perovskite La0.6Sr 0.4Cr1− xCoxO3−δ solid solutions for solar-thermochemical fuel production: strategies to lower the operation temperature. Journal of Materials Chemistry A, 2015. 3(30): p. 15546-15557. 3. Scheffe, J.R., D. Weibel, and A. Steinfeld, Lanthanum–Strontium–Manganese Perovskites as Redox Materials for Solar Thermochemical Splitting of H2O and CO2. Energy & Fuels, 2013. 27(8): p. 4250-4257. 4. Yang, C.-K., et al., Thermodynamic and kinetic assessments of strontium-doped lanthanum manganite perovskites for two-step thermochemical water splitting. Journal of Materials Chemistry A, 2014. 2(33): p. 13612-13623

Plastic Deformation Behavior in Steels during Metal Forming Processes: A Review

The plastic deformation occurs in steels during metal forming processing such as rolling, forging, high-pressure torsion, etc. which modify mechanical properties of materials through the grain refinement, and the shape change of objects. Several phenomena in the scope of plastic deformation, such as hardening, recovery, and recrystallization are of great importance in designing thermomechanical processing. During the last decades, a focus of research groups has been devoted particularly to the field of metals processing of steel parts through plastic deformation combined with specific heat treatment conditions. In this review chapter, the current status of research work on the role of plastic deformation during manufacturing is illuminated

Analysis and Modeling of Stress–Strain Curves in Microalloyed Steels Based on a Dislocation Density Evolution Model

Microalloyed steels offer a good combination of desirable mechanical properties by fine-tuning grain growth and recrystallization dynamics while keeping the carbon content low for good weldability. In this work, the dislocation density evolution during hot rolling was correlated by materials modeling with flow curves. Single-hit compression tests at different temperatures and strain rates were performed with varying isothermal holding times prior to deformation to achieve different precipitation stages. On the basis of these experimental results, the dislocation density evolution was evaluated using a recently developed semi-empirical state-parameter model implemented in the software MatCalc. The yield stress at the beginning of the deformation σ0, the initial strain hardening rate θ0, and the saturation stress σ∞—as derived from the experimental flow curves and corresponding Kocks plots—were used for the calibration of the model. The applicability for industrial processing of many microalloyed steels was assured by calibration of the model parameters as a function of temperature and strain rate. As a result, it turned out that a single set of empirical equations was sufficient to model all investigated microalloyed steels since the plastic stresses at high temperatures did not depend on the precipitation state

Thermodynamic modeling of G-phase and assessment of phase stabilities in reactor pressure vessel steels and cast duplex stainless steels

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