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At least 127 records · Page 7

Effect of thickness on degradation of austenitic 347H steel by direct-fired supercritical CO 2 power cycle environment

Austenitic 347H steel of two thicknesses (2.54 and 0.6 mm) was exposed to a simulated direct-fired supercritical CO 2 (sCO 2 ) power cycle environment at 650°C and 1 atm for 1000 h then tensile stressed at room temperature to study the deformation behavior. The thicker 347H formed a protective chromia scale over most of the surface, which minimized carburization of the underlying steel and resulted in no change in mechanical performance. In stark contrast, the thinner 347H formed non-protective Fe-rich oxides over the entire surface, resulting in extensive carburization of the underlying steel. Finally, this led to increased strength but significantly reduced ductility, resulting in partially brittle failure

36 MATERIALS SCIENCE↗

One-dimensional, transient modeling of a fixed-bed regenerator as a replacement for recuperators in supercritical CO 2 power cycles

Fixed-bed regenerators may be a low cost alternative to recuperators for supercritical CO 2 power cycles. However, the transient nature of regenerators operating in sCO 2 power cycles has not been previously characterized. This study details a one-dimensional, transient model of a fixed-bed regenerator that captures phenomena such as local fluid properties and heat transfer coefficients, entrained fluid heat capacity, and the effects of conservation of mass during process switching. The model is validated with experimental results of a 10 kWth regenerator. This comparison shows that the model predicts temperature as a function of both time and space exceptionally well. The model predicts effectiveness, heat transfer, and discharge temperatures within 5%, and predicts pressure drop and fluid carryover within 10%. This model could be used in future studies to simulate regenerators within a supercritical CO 2 power cycle.

30 DIRECT ENERGY CONVERSION↗

Multiscale characterization of an additively manufactured property graded Ni-base alloy for molten-salts\supercritical-CO 2 heat exchangers

The sequential optimization of strength and corrosion resistance in conventional alloy design procedures often results in a tradeoff between environmental degradation and optimal mechanical properties. A concurrent optimization of these two material properties is essential to efficiently develop high temperature alloys that can withstand harsh environments increasingly required for carbon–neutral energy technologies. In this work, we demonstrate the feasibility of directed energy deposition (DED) to manufacture a dual-corrosion resistant Ni-based alloy (Hastelloy N and Haynes 282), that meets the high temperature operation requirements of a molten-salts\supercritical-CO 2 (sCO 2 ) heat exchanger. A combination of multiscale characterization techniques and computational thermodynamics was employed to evaluate the cracking susceptibilities during fabrication and predict the microstructural stability of the material. Very good agreement was achieved between the observed and predicted phases and phase fractions of the as-printed material. A careful characterization of the transition zone between the two terminal alloy chemistries revealed potential precipitation strengthening (γ') on the Hastelloy N side while columnar-shaped M 23 C 6 and γ' precipitates that formed at grain boundaries (GBs) of the transition zone likely minimized the local interfacial energies. Both these mechanisms are believed to increase the interfacial stability but their performance at high temperatures requires further investigation.

36 MATERIALS SCIENCE↗

The performance of additively manufactured Haynes 282 in supercritical CO 2

The use of supercritical carbon dioxide (sCO 2 ) as a working fluid is garnering interest in next generation power production systems due to the possibility of increased operational efficiencies and lower associated costs. Its implementation requires alloys with excellent high temperature strength and corrosion resistance, which makes Haynes 282® (H282) a suitable candidate. With increasing adoption of additive manufacturing (AM) in the energy industry, there is a need to investigate long-term sCO2 exposure on AM produced materials. Additively manufactured H282 (AM-H282) samples built using laser powder bed fusion in two different orientations were analyzed through imaging, gravimetric analysis, and room-temperature tensile testing before and after 1000-h exposure to CO 2 at 750 °C and 20 MPa. Performed imaging included observation of the sample surfaces and of the material bulk (cross sections) through means of Scanning Electron Microscopy (SEM) and optical microscopy. In comparison to wrought H282, it was found that the exposed material exhibited a similar Cr 2 O 3 oxide protective layer about 2 μm in thickness with additional top-surface TiO 2 oxide and carbon-rich precipitates. It was also similarly observed that internal oxidation was present but limited to a depth of 20 μm, and a 1–3 μm γ’ denuded region appeared to surround all internal and surface oxidation. Thermal aging effects were noted with the precipitation of needle-like structures in the γ/γ’ matrix and a coarsening of the γ’ precipitates from 28 nm to 73 nm. Mass measurements analyzing oxide precipitation revealed a larger increase compared to wrought, representing an approximate 20% difference. Tensile testing results showed similar behavior to wrought with a slight increase in yield strength and a large reduction in elongation in the exposed samples.

36 MATERIALS SCIENCE↗

Shock tube/laser absorption measurement of the rate constant of the reaction: H 2 O 2 + CO 2 2OH + CO 2

We address the role of the linear mixing rule in the kinetics of the H 2 O 2 decomposition system by reporting the rate constant for H 2 O 2 + M = 2OH + M (M = Ar and CO 2 ) in the temperature range of 1087-1234 K at low pressures in a mixture of 20% CO 2 in Argon. The reaction rate constant was inferred from H 2 O concentrations monitored by using a laser-absorption spectroscopy-based water diagnostic. To the best of our knowledge, this is the first measurement of the rate constant of this reaction in a mixture to be reported in literature. A significant discrepancy was found between the rate constants derived using the traditional linear mixing rule and the reduced pressure linear mixing rule. Furthermore, this discrepancy can have serious implications on the predictive accuracy of these kinetic models, especially under conditions relevant to the operation of supercritical CO 2 (sCO 2 ) power cycles that rely on oxy-fuel combustion in a working fluid comprised almost entirely of CO 2 .

20 FOSSIL-FUELED POWER PLANTS↗

Dimensional Control of Octahedral Tilt in SrRuO 3 via Infinite-Layered Oxides

Manipulation of octahedral distortion at atomic scale is an effective means to tune the ground states of functional oxides. Previous work demonstrates that strain and film thickness are variable parameters to modify the octahedral parameters. However, selective control of bonding geometry by structural propagation from adjacent layers is rarely studied. Here we propose a new route to tune the ferromagnetism in SrRuO 3 (SRO) ultrathin layers by oxygen coordination of adjacent SrCuO 2 (SCO) layers. The infinite-layered CuO 2 exhibits a structural transformation from “planar-type” to “chain-type” with reduced film thickness. Two orientations dramatically modify the polyhedral connectivity at the interface, thus altering the octahedral distortion of SRO. The local structural variation changes the spin state of Ru and orbital hybridization strength, leading to a significant change in the magnetoresistance and anomalous Hall resistivity. Furthermore, these findings could launch investigations into adaptive control of functionalities in quantum oxide heterostructures using oxygen coordination.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Observing the Surface Termination of LaScO 3 Perovskite Using Solid-State Nuclear Magnetic Resonance

Materials with well-defined surfaces are drawing increased attention for the design of bespoke catalysts and nanomaterials. Gaining a detailed understanding of the surfaces of these materials is an important challenge, which is often complicated by surface polymorphism and dynamic restructuring. We introduce the use of surface-enhanced NMR spectroscopy for the observation of such surfaces, focusing on LaScO 3 as an example. Here, we show that double-resonance NMR experiments correlating surface oxygen and probe molecules to the 139 La and 45 Sc nuclei at the surface reveal the material to be terminated by a ScO x monolayer. Surface-selective 17 O and 45 Sc NMR experiments further showed the material to be hydroxyl terminated and that the surface may be prone to dynamic restructuring as a result of moisture exposure. Perhaps most interestingly, surface-selective 139 La NMR experiments revealed the existence of previously undetected surface lanthanum defects, suggesting that surface-enhanced NMR may be useful as a guide in the synthesis of defect-free surfaces in the design of various nanomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Manipulating electron redistribution to achieve electronic pyroelectricity in molecular [FeCo] crystals

Pyroelectricity plays a crucial role in modern sensors and energy conversion devices. However, obtaining materials with large and nearly constant pyroelectric coefficients over a wide temperature range for practical uses remains a formidable challenge. Attempting to discover a solution to this obstacle, we combined molecular design of labile electronic structure with the crystal engineering of the molecular orientation in lattice. This combination results in electronic pyroelectricity of purely molecular origin. Here, we report a polar crystal of an [FeCo] dinuclear complex exhibiting a peculiar pyroelectric behavior (a substantial sharp pyroelectric current peak and an unusual continuous pyroelectric current at higher temperatures) which is caused by a combination of Fe spin crossover (SCO) and electron transfer between the high-spin Fe ion and redox-active ligand, namely valence tautomerism (VT). As a result, temperature dependence of the pyroelectric behavior reported here is opposite from conventional ferroelectrics and originates from a transition between three distinct electronic structures. The obtained pyroelectric coefficient is comparable to that of polyvinylidene difluoride at room temperature.

36 MATERIALS SCIENCE↗

Identifying geologic characteristics and operational decisions to meet global carbon sequestration goals

Geologic carbon sequestration is the process of injecting and storing CO 2 in subsurface reservoirs and is an essential technology for global environmental security (e.g., climate change mitigation) and economic security (e.g., CO 2 tax credits). To meet energy, economic, and environmental goals, society will have to identify vast volumes of high-capacity, low-cost, and viable storage reservoirs for sequestering CO 2 . In turn, this requires understanding how major geologic characteristics (such as reservoir depth, thickness, permeability, porosity, and temperature) and design and operational decisions (such as injection well spacing) impact CO 2 injection rates, storage capacity, and economics. Although many numerical simulation tools exist, they cannot repeat the required thousands or millions of simulations to identify ideal reservoir properties and the sensitivity and interaction between geologic parameters and operational decisions. Here, we use SCO 2 T—a fast-running, reduced-order modeling framework—to explore the sensitivity of major geologic parameters and operational decisions to engineering (CO 2 injection rates, plume dimensions, and storage capacities and effectiveness) and costs. Our results show, for the first time, benefits and impacts such as allowing CO 2 plumes to overlap, how different well spacing patterns affect CO 2 sequestration, the effects on costs of including brine treatment and disposal, and the effect of restricting injection rates to 1 MtCO 2 per y based on well limitations. We reveal multiple novel and unintuitive findings including: (i) deeper reservoirs have reduced carbon sequestration costs until injection rates reach 1 MtCO 2 per y, at which point deeper reservoirs become more expensive, (ii) thicker formations allow for increased injection rates and storage capacity, but thickness barely impacts plume areas, (iii) higher geothermal gradients result in reduced sequestration costs, unless brine treatment/disposal costs are included, at which point reservoirs having lower geothermal gradients are more economical because they produce less brine for each unit of injected CO 2 , and (iv) allowing plumes to overlap has a significantly positive impact of increasing storage capacities but has only a small influence on reducing sequestration costs. Altogether, our results illustrate new scientific conclusions to help identify suitable sites to inject and store CO 2 , to help understand the complex interaction between geology and resulting costs, and to help support the pursuit of meeting global sequestration targets.

58 GEOSCIENCES↗

CASPT2 molecular geometries of Fe( II ) spin-crossover complexes

Using fully internally contracted (FIC)-CASPT2 analytical gradients, geometry optimizations of spin-crossover complexes are reported. This approach is tested on a series of Fe(II) complexes with different sizes, ranging from 13 to 61 atoms. A combination of active space and basis set choices are employed to investigate their role in determining reliable molecular geometries. The reported strategy demonstrates that a wave function-based level of theory can be used to optimize the geometries of metal complexes in reasonable times and enables one to treat the molecular geometry and electronic structure of the complexes using the same level of theory. For a series of smaller Fe(II) SCO complexes, strong field ligands in the LS state result in geometries with the largest differences between DFT and CASPT2; however, good agreement overall is observed between DFT and CASPT2. For the larger complexes, moderate sized basis sets yield geometries that compare well with DFT and available experimental data. Here we recommend using the (10e,12o) active space since convergence to a minimum structure was more efficient than with truncated active spaces despite having similar Fe–ligand bond distances.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self-assembly of a supramolecular spin-crossover tetrahedron

A new mononuclear iron(ii) SCO compound featuring H-bonding donor and acceptor units provides an entry to a purely supramolecular switchable {Fe 4 } tetrahedron that exhibits a singular magnetic behavior for each of the four Fe(ii) centers.

Chemistry↗

Defining a compact dry cooler design to reduce LCOE contribution in a CSP facility

Concentrating solar power (CSP), when coupled with a supercritical carbon dioxide (sCO 2 ) power cycle and sensible heat storage, presents a renewable and clean alternative for utility-scale power generation. However, in order to be competitive in the current and future markets, CSP facilities must limit their levelized cost of electricity (LCOE) by minimizing capital costs and reducing operating costs over the lifetime of the plant. Targeting this goal, this study investigates the LCOE impact of the power cycle pre-cooler. This study considers a compact dry cooler with micro-channel technology on the CO 2 side and formed fin geometry on the air side, using directly-coupled centrifugal fans and a transition duct to improve air distribution across the fins as well as protect the fins from contaminants which may cause blockage, soiling, fouling, and damage. In an effort to better understand the dry cooler impact on LCOE, a sensitivity study was conducted using various combinations of end-to-end approach temperatures, air-side pressure drop values, CO 2 -side pressure drop values, fan types, cooler turndown control schemes, cooler module sizes, and design-point ambient temperatures. Furthemore, off-design cycle performance data was calculated for each dry cooler design using NPSS simulation software; cycle performance data were then input to System Advisor Model (SAM) along with the associated capital costs for LCOE prediction of a 100 MW system over a 30 year plant lifetime. Results of this study show the LCOE is most sensitive to air-side performance, followed by heat transfer effectiveness and capital cost. It was found that a power cycle with a mid- to high-performance dry cooler will produce the most competitive power-production costs. Designing at the extreme ends for approach temperature (or effectiveness), design-point ambient temperature, and compactness (footprint) produce higher LCOE values; mid-range values for these parameters balance performance, operating costs, and associated capital cost to optimize LCOE.

14 SOLAR ENERGY↗

Direct observation of the magnetic anisotropy of an Fe(II) spin crossover molecular thin film

Abstract In this work, we provide clear evidence of magnetic anisotropy in the local orbital moment of a molecular thin film based on the SCO complex [Fe(H 2 B(pz) 2 ) 2 (bipy)] (pz = pyrazol−1−yl, bipy = 2,2′−bipyridine). Field dependent x-ray magnetic circular dichroism measurements indicate that the magnetic easy axis for the orbital moment is along the surface normal direction. Along with the presence of a critical field, our observation points to the existence of an anisotropic energy barrier in the high-spin state. The estimated nonzero coupling constant of ∼2.47 × 10 −5 eV molecule −1 indicates that the observed magnetocrystalline anisotropy is mostly due to spin–orbit coupling. The spin- and orbital-component anisotropies are determined to be 30.9 and 5.04 meV molecule −1 , respectively. Furthermore, the estimated g factor in the range of 2.2–2.45 is consistent with the expected values. This work has paved the way for an understanding of the spin-state-switching mechanism in the presence of magnetic perturbations.

74 ATOMIC AND MOLECULAR PHYSICS↗

High-precision mass measurements of the isomeric and ground states of 44 V: Improving constraints on the isobaric multiplet mass equation parameters of the A=44, 0 + quintet

Background: The quadratic isobaric multiplet mass equation (IMME) has been very successful at predicting the masses of isobaric analog states in the same multiplet, while its coefficients are known to follow specific trends as functions of mass number. The Atomic Mass Evaluation 2016 [Chin. Phys. C 41, 030003 (2017)] 44 V mass value results in an anomalous negative c coefficient for the IMME quadratic term; a consequence of large uncertainty and an unresolved isomeric state. The b and c coefficients can provide useful constraints for construction of the isospin-nonconserving Hamiltonians for the pf shell. In addition, the excitation energy of the 0 + , T = 2 level in 44 V is currently unknown. This state can be used to constrain the mass of the more exotic 44 Cr. Purpose: The aim of the experimental campaign was to perform high-precision mass measurements to resolve the difference between 44 V isomeric and ground states, to test the IMME using the new ground state mass value and to provide necessary ingredients for the future identification of the 0 + , T = 2 state in 44 V. Method: High-precision Penning trap mass spectrometry was performed at LEBIT, located at the National Superconducting Cyclotron Laboratory, to measure the cyclotron frequency ratios of [ 44g,m VO] + versus [ 32 SCO] + , a well-known reference mass, to extract both the isomeric and ground state masses of 44 V. Results: The mass excess of the ground and isomeric states in 44 V were measured to be -23 804.9(80) keV/c 2 and -23 537.0(55) keV/c 2 , respectively. This yielded a new proton separation energy of S p = 1 773(10) keV. Conclusion: The new values of the ground state and isomeric state masses of 44 V have been used to deduce the IMME b and c coefficients of the lowest 2 + and 6 + triplets in A = 44. The 2 + c coefficient is now verified with the IMME trend for lowest multiplets and is in good agreement with the shell-model predictions using charge-dependent Hamiltonians. The mirror energy differences were determined between 44 V and 44 Sc, in line with isospin-symmetry for this multiplet. Finally, the new value of the proton separation energy determined, to an uncertainty of 10 keV, will be important for the determination of the 0 + , T = 2 state in 44 V and, consequently, for prediction of the mass excess of 44 Cr.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Probing the Effects of NO x and SO x Impurities on Oxy-Fuel Combustion in Supercritical CO 2 : Shock Tube Experiments and Chemical Kinetic Modeling

The direct-fired supercritical carbon dioxide cycles are one of the most promising power generation methods in terms of their efficiency and environmental friendliness. Two important challenges in implementing these cycles are the high pressure (300 bar) and high CO 2 dilution (>80%) in the combustor. The design and development of supercritical oxy-combustors for natural gas require accurate reaction kinetic models to predict the combustion outcomes. The presence of a small amount of impurities in natural gas and other feed streams to oxy-combustors makes these predictions even more complex. During oxy-combustion, trace amounts of nitrogen present in the oxidizer is converted to NO x and gets into the combustion chamber along with the recirculated CO 2 . Similarly, natural gas can contain a trace amount of ammonia and sulfurous impurities that get converted to NO x and SO x and get back into the combustion chamber with recirculated CO 2 . In this work, a reaction model is developed for predicting the effect of impurities such as NO x and SO x on supercritical methane combustion. The base mechanism used in this work is GRI Mech 3.0. H 2 S combustion chemistry is obtained from Bongartz et al. while NOx chemistry is from Konnov. The reaction model is then optimized for a pressure range of 30–300 bar using high-pressure shock tube data from the literature. It is then validated with data obtained from the literature for methane combustion, H 2 S oxidation, and NO x effects on ignition delay. The effect of impurities on CH 4 combustion up to 16 atm is validated using NO x -doped methane studies obtained from the literature. In order to validate the model for high-pressure conditions, experiments are conducted at the UCF shock tube facility using natural gas identical mixtures with N 2 O as an impurity at ~100 bar. Current results show that there is a significant change in ignition delay with the presence of impurities. A comparison is made with experimental data using the developed model and predictions are found to be in good agreement. The model developed was used to study the effect of impurities on CO formation from sCO 2 combustors. It was found that NO x helps in reducing CO formation while the presence of H 2 S results in the formation of more CO. The reaction mechanism developed herein can also be used as a base mechanism to develop reduced mechanisms for use in CFD simulations.

Energy & Fuels↗

A High-Fidelity Modeling Tool to Support the Design of Oxy-Combustors for Direct-Fired Supercritical CO2 Cycles

The challenge in the design of oxy-combustors for direct-fired supercritical CO 2 (sCO 2 ) cycles is in addressing disparate performance metrics and objectives. Key design parameters to consider include, among others, injector design for mixing and flame stability, split of recycled CO 2 diluent between injectors and cooling films, target flame temperatures to control noncondensable products, and strategies to inject the diluent CO 2 for film cooling and thermal control. In order to support novel oxy-combustor designs, a high-fidelity yet numerically efficient modeling framework based on the CRUNCH CFD® flow solver is presented, featuring key physics-based submodels relevant in this regime. For computational efficiency in modeling large kinetic sets, a flamelet/progress variable (FPV) based tabulated-chemistry approach is utilized featuring a three-stream extension to allow for the simulation of the CO 2 film cooling stream in addition to the fuel and oxidizer streams. Finite rate chemistry effects are modeled in terms of multiple progress variables for the primary flame as well as for slower-evolving chemical species such as NO x and SO x contaminants. Real fluid effects are modeled using advanced equations of states. The predictive capabilities of this computationally tractable design support tool are demonstrated on a conceptual injector design for an oxy-combustor operating near 30 MPa. Simulations results provide quantitative feedback on the effectiveness of the film cooling as well as the level of contaminants (CO, NO, and N) in the exhaust due to impurities entering from the injectors. These results indicate that this framework would be a useful tool for refining and optimizing the oxy-combustor designs as well as risk mitigation analyses.

Engineering↗

Investigation of Gas Turbine Internal Cooling Using Supercritical CO 2 —Effect of Surface Roughness and Channel Aspect Ratio

In this paper, an experimental and numerical investigation of internal cooling channels with rib turbulators is presented with sCO 2 as the working fluid at process conditions (pressure-20.7 MPa and temperature up to 150 °C). The effect of channel aspect ratio up to 2:1 on thermal-hydraulic performance is explored in additively manufactured rectangular channels and square channels, both with and without 60 deg ribs on the top and bottom sides. The Wilson-plot method is employed to experimentally measure channel-averaged Nusselt number over a Reynolds number range up to 370,000. The friction factor is calculated from pressure drop and mass flow rate and additionally, the overall thermal performance factor (TPF) is reported. A companion computational fluid dynamics (CFD) simulation is performed for the rib turbulated cooling configurations reported in the experiments using the Reynolds average Navier–Stokes-based turbulence model. The objective of the numerical study is to gain insight into the local heat transfer augmentation in the ribbed channels as a result of varying the aspect ratio, channel configuration (square versus rectangular), operating conditions (Reynolds number) and the surface roughness, an inherent outcome of the additive manufacturing process. Surface roughness is simulated using sand grain roughness height (K S ) calculated from the experimental data, and a comparison is presented with the corresponding channel configuration with varying surface roughness heights starting from smooth surfaces (K S = 0). Experimental results indicate that the heat transfer augmentation is negligible in the rectangular channels with ribs on the long side compared to the square channel. However, it is enhanced by 60% in comparison to placing ribs on the shorter side. The TPF remains constant at around 1 for the entire range of Reynolds numbers consistent with prior work at the National Energy Technology Laboratory (NETL). Here, the simulation results highlight that increased surface roughness can have a favorable considerable influence on Nusselt number and overall thermal performance enhancement.

42 ENGINEERING↗

Helical Fins for Concentrated Solar Receivers: Design Optimization and Entropy Analysis

Concentrated solar power (CSP) with thermal energy storage (TES) has the potential to achieve grid parity. This can be realized by operating CSP systems at temperatures above 700 °C with high-efficiency sCO 2 power cycles. However, operating CSP systems at such temperatures poses several challenges, among which the design of solar receivers to accommodate increased thermal loads is critical. To this end, this work explores and optimizes various swirl-inducing internal fin designs for solar receiver tubes. These fin designs not only improve the thermal performance of receiver tubes but also levelize temperature unevenness caused by non-uniform thermal loading. In this work, the geometric parameters of the fin designs are optimized to maximize the Nusselt number with a constraint on the friction factor. This optimization, however, is computationally intensive, requiring hundreds of simulation calls to computational fluid dynamics (CFD) models. Here, to circumvent this problem, surrogate models are used to approximate the simulation outputs needed during the optimization. In addition, this study also examines the fin designs from an entropy generation perspective. To this end, the entropy contributions from thermal and viscous effects are quantitatively compared while varying the operational Reynolds number.

14 SOLAR ENERGY↗