Development and prototype testing of MgCl2/graphite foam latent heat thermal energy storage system
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Singh, Dileep↗
SEARCH · Engineering Papers
Results for “thermalization”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Optical properties and thermal stability of Cu spinel oxide nanoparticle solar absorber coatings
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Energy & Fuels↗
Thermal Activation of Zirconium(IV) Acetylacetonate Catalysts to Enhance Polyurethane Synthesis and Reprocessing
Carbamate formation and exchange catalysts enable efficient polyurethane (PU) manufacturing, as well as emerging recycling and reprocessing methods for PU thermosets. Zirconium β-diketonate complexes, such as Zr acetylacetonate [Zr(acac) 4 ], are effective alternatives to toxic organotin catalysts that have been used for PU reprocessing. Here, we report that Zr(acac) 4 undergoes a thermally activated process in the PU network during reprocessing that transforms it into a more active carbamate exchange catalyst. This process is associated with the irreversible loss of acetylacetonate ligands and is not observed for the more sterically hindered Zr 2,2,6,6-tetramethyl-3,5-heptanedione [Zr(tmhd) 4 ] complex. Crossover experiments between PU thermoplastics indicated enhanced carbamate exchange after the thermal activation of Zr(acac) 4 in the presence of one of the PUs, whereas a sample of Zr(acac) 4 activated in the absence of the PU had no catalytic activity. Thermal gravimetric analysis suggested that this process is associated with the loss of one protonated acac ligand. Stress relaxation analysis of PU thermosets indicated a distinct change in the characteristic relaxation time associated with the thermal activation of Zr(acac) 4 at temperatures above 140 °C; no such change was observed for samples reprocessed using Zr(tmhd) 4 . Density functional theory and molecular experiments suggest that irreversible ligand exchange of acac with alkoxide or carbamate reduces the activation energy for urethane formation and reversion. Furthermore, the Zr(acac) 4 catalyst activated in the presence of a PU’s polyol precursor provided more porous and less dense PU foams compared to those made using the unactivated Zr(acac) 4 catalyst. Furthermore, these findings are important for developing improved PU synthesis and recycling processes. Thermally activating a catalyst during reprocessing may provide more nuanced control of the in-use and reprocessing characteristics of PU thermosets.
Alcohols↗
Thermal and Non-thermal Physiochemical Processes in Nanoscale Films of Amorphous Solid Water
Amorphous solid water (ASW) is a metastable form of water created by vapor deposition onto a cold substrate (typically less than 130 K). Since this unusual form of water only exists on earth in laboratories with highly specialized equipment, it is fair to ask why there is any interest in studying this esoteric material. Much of the scientific interest involves using ASW as a model system to explore the physical and reactive properties of liquid water and aqueous solutions. Other researchers are interested in ASW because it is believed to be the predominate form of water in the extreme cold temperatures found in many astrophysical and planetary environments. In addition, ASW is a convenient model system for studying the stability of metastable systems (glasses) and the properties of highly porous materials. A fundamental understanding of such properties has applications in a diverse range of disciplines including cryobiology, food science, pharmaceuticals, astrophysics and nuclear waste storage among others.There exist several excellent reviews on the properties of ASW and supercooled liquid water and a new comprehensive review is beyond the scope of this Account. Instead, we focus on our research over the past 15 years using molecular beams and surface science techniques to probe the thermal and non thermal properties of nanoscale films of ASW. We use molecular beams to precisely control the deposition conditions (flux, incident, energy, incident angle) to create compositionally-tailored, nanoscale films of ASW at low temperatures. To study the transport properties (viscosity, diffusivity), the amorphous films can be heated above their glass transition temperatures, Tg, at which time they transform into deeply supercooled liquids prior to crystallization. The advantage of this approach is that at temperatures near Tg the viscosity is approximately 15 orders of magnitude larger than a normal liquid, and therefore the crystallization kinetics are dramatically slowed, increasing the time available for experiments. For example, near Tg, on a typical laboratory time scale (e.g. {approx}1000 s), a water molecule moves less than a molecular distance. For this reason, nanoscale films help to probe the behavior and reactions of supercooled liquid at these low temperatures. ASW films can be used for investigating the non-thermal reactions relevant to radiolysis. In this account we will present a survey of our research on the thermal and non thermal properties of ASW using this approach.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Structural and thermal properties of ultralow thermal conductivity Ba 3 Cu 2 Sn 3 Se 10
The thermal properties of Ba 3 Cu 2 Sn 3 Se 10 were investigated by measurement of the thermal conductivity and heat capacity. The chemical bonding in this diamagnetic material was investigated using structural data from Rietveld refinement and calculated electron localization. This quaternary chalcogenide is monoclinic (P2 1 /c), has a large unit cell with 72 atoms in the primitive cell, and a high local coordination environment. Additionally, the Debye temperature (162 K) and average speed of sound (1666 m s -1 ) are relatively low with a very small electronic contribution to the heat capacity. Ultralow thermal conductivity (0.46 W m -1 K -1 at room temperature) is attributed to the relatively weak chemical bonding and intrinsic anharmonicity, in addition to a large unit cell. This work is part of the continuing effort to explore quaternary chalcogenides with intrinsically low thermal conductivity and identify the features that result in a low thermal conductivity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The role of higher-order modes on the electromagnetic whistler-cyclotron wave fluctuations of thermal and non-thermal plasmas
Two fundamental challenging problems of laboratory and astrophysical plasmas are the understanding of the relaxation of a collisionless plasmas with nearly isotropic velocity distribution functions and the resultant state of nearly equipartition energy density with electromagnetic plasma turbulence. Here, we present the results of a study which shows the role that higher-order-modes play in limiting the electromagnetic whistler-like fluctuations in a thermal and non-thermal plasma. Our main results show that for a thermal plasma the magnetic fluctuations are confined by regions that are bounded by the least-damped higher order modes. We further show that the zone where the whistler-cyclotron normal modes merges the electromagnetic fluctuations shifts to longer wavelengths as the β{sub e} increases. This merging zone has been interpreted as the beginning of the region where the whistler-cyclotron waves losses their identity and become heavily damped while merging with the fluctuations. Our results further indicate that in the case of nonthermal plasmas, the higher-order modes do not confine the fluctuations due to the effective higher-temperature effects and the excess of suprathermal plasma particles. The analysis presented here considers the second-order theory of fluctuations and the dispersion relation of weakly transverse fluctuations, with wave vectors parallel to the uniform background magnetic field, in a finite temperature isotropic bi-Maxwellian and Tsallis-kappa-like magnetized electron–proton plasma. Our results indicate that the spontaneously emitted electromagnetic fluctuations are in fact enhanced over these quasi modes suggesting that such modes play an important role in the emission and absorption of electromagnetic fluctuations in thermal or quasi-thermal plasmas.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Quantification of thermal and contact resistances of scanning thermal probes
Scanning thermal probes are widely used for imaging temperature fields with nanoscale resolution, for studying near-field radiative heat transport and for locally heating samples. In all these applications, it is critical to know the thermal resistance to heat flow within the probe and the thermal contact resistance between the probe and the sample. Here, we present an approach for quantifying the aforementioned thermal resistances using picowatt resolution heat flow calorimeters. The measured contact resistance is found to be in good agreement with classical predictions for thermal contact resistance. The techniques developed here are critical for quantitatively probing heat flows at the nanoscale.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Thermal conductivity in self-assembled CoFe 2 O 4 /BiFeO 3 vertical nanocomposite films
The thermal conductivity of self-assembled nanocomposite oxide films consisting of cobalt ferrite (CFO) spinel pillars grown within a single-crystal bismuth ferrite (BFO) perovskite matrix is described as a function of the volume fraction of the spinel. Single phase BFO and CFO had cross-plane thermal conductivities of 1.32 W m –1 K –1 and 3.94 W m –1 K –1 , respectively, and the thermal conductivity of the nanocomposites increased with the CFO volume fraction within this range. A small increase (~5%) in thermal conductivity for the pure CFO phase in the AC-demagnetized state was observed, suggesting possible magnon contributions. As a result, steady state gray-medium based variance-reduced Monte Carlo simulations show consistent trends with experimental data on the dependence of thermal conductivity with the CFO volume fraction.
36 MATERIALS SCIENCE↗
Thermal transport in nanoporous holey silicon membranes investigated with optically induced transient thermal gratings
In this study, we use transient thermal gratings—a non-contact, laser-based thermal metrology technique with intrinsically high accuracy—to investigate room-temperature phonon-mediated thermal transport in two nanoporous holey silicon membranes with limiting dimensions of 120 nm and 250 nm, respectively. We compare the experimental results with ab initio calculations of phonon-mediated thermal transport according to the phonon Boltzmann transport equation (BTE) using two different computational techniques. We find that the calculations conducted within the Casimir framework, i.e., based on the BTE with the bulk phonon dispersion and diffuse scattering from surfaces, are in quantitative agreement with the experimental data and thus conclude that this framework is adequate for describing phonon-mediated thermal transport in silicon nanostructures with feature sizes of the order of 100 nm.
Duncan, Ryan A. (ORCID:0000000328318099)↗
Structured illumination with thermal imaging (SI-TI): A dynamically reconfigurable metrology for parallelized thermal transport characterization
The recent push for the “materials by design” paradigm requires synergistic integration of scalable computation, synthesis, and characterization. Among these, techniques for efficient measurement of thermal transport can be a bottleneck limiting the experimental database size, especially for diverse materials with a range of roughness, porosity, and anisotropy. Traditional contact thermal measurements have challenges with throughput and the lack of spatially resolvable property mapping, while non-contact pump-probe laser methods generally need mirror smooth sample surfaces and also require serial raster scanning to achieve property mapping. Here, we present structured illumination with thermal imaging (SI-TI), a new thermal characterization tool based on parallelized all-optical heating and thermometry. Experiments on representative dense and porous bulk materials as well as a 3D printed thermoelectric thick film (~50 μm) demonstrate that SI-TI (1) enables paralleled measurement of multiple regions and samples without raster scanning; (2) can dynamically adjust the heating pattern purely in software, to optimize the measurement sensitivity in different directions for anisotropic materials; and (3) can tolerate rough (~3 μm) and scratched sample surfaces. Here, this work highlights a new avenue in adaptivity and throughput for thermal characterization of diverse materials.
42 ENGINEERING↗
Generalized Procedure for Improved Accuracy of Thermal Contact Resistance Measurements for Materials With Arbitrary Temperature-Dependent Thermal Conductivity
Thermal contact resistance (TCR) is most commonly measured using one-dimensional steady-state calorimetric techniques. In the experimental methods we utilized, a temperature gradient is applied across two contacting beams and the temperature drop at the interface is inferred from the temperature profiles of the rods that are measured at discrete points. During data analysis, thermal conductivity of the beams is typically taken to be an average value over the temperature range imposed during the experiment. Our generalized theory is presented and accounts for temperature-dependent changes in thermal conductivity. The procedure presented enables accurate measurement of TCR for contacting materials whose thermal conductivity is any arbitrary function of temperature. For example, it is shown that the standard technique yields TCR values that are about 15% below the actual value for two specific examples of copper and silicon contacts. Conversely, the generalized technique predicts TCR values that are within 1% of the actual value. The method is exact when thermal conductivity is known exactly and no other errors are introduced to the system.
42 ENGINEERING↗
Suppression of Electron Thermal Conduction by Whistler Turbulence in a Sustained Thermal Gradient
The dynamics of weakly magnetized collisionless plasmas in the presence of an imposed temperature gradient along an ambient magnetic field is explored with particle-in-cell simulations and modeling. Two thermal reservoirs at different temperatures drive an electron heat flux that destabilizes off-angle whistler-type modes. The whistlers grow to large amplitude, δB/B 0 ≃ 1, and resonantly scatter the electrons, significantly reducing the heat flux. Interestingly, the resulting steady-state heat flux is largely independent of the thermal gradient. The rate of thermal conduction is instead controlled by the finite propagation speed of the whistlers, which act as mobile scattering centers that convect the thermal energy of the hot reservoir. The findings are relevant to thermal transport in high-β astrophysical plasmas such as hot accretion flows and the intracluster medium of galaxy clusters.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Low Thermal Conductivity, High Durability Thermal Barrier Coatings for IGCC Environments
Advanced thermal barrier coatings (TBC) are crucial to improved energy efficiency in next generation gas turbine engines. The use of traditional topcoat materials, e.g. yttria-stabilized zirconia (YSZ), is limited at elevated temperatures due to (1) the accelerated undesirable phase transformations and (2) corrosive attacks by calcium-magnesium-aluminum-silicate (CMAS) deposits and moisture. The first goal of this project is to use the Solution Precursor Plasma Spray (SPPS) process to further reduce the thermal conductivity of YSZ TBCs by introducing a unique microstructural feature of layered porosity, called inter-pass boundaries (IPBs). Extensive process optimization accompanied with hundreds of spray trials as well as associated SEM cross-section and laser-flash measurements, yielded a thermal conductivity as low as 0.62 Wm⁻¹K⁻¹ in SPPS YSZ TBCs, approximately 50% reduction of APS TBCs; while other engine critical properties, such as cyclic durability, erosion resistance and sintering resistance, were characterized to be equivalent or better than APS baselines. In addition, modifications were introduced to SPPS TBCs so as to enhance their resistance to CMAS under harsh IGCC environments. Several mitigation approaches were explored, including doping the coatings with Al₂O₃ and TiO₂, applying a CMAS infiltration-inhibiting surface layer, and filling topcoat cracks with blocking substances. The efficacy of all these modifications was assessed with a set of novel CMAS-TBC interaction tests, and the moisture resistance was tested in a custom-built high-temperature moisture rig. In the end, the optimal low thermal conductivity TBC system was selected based on all evaluation tests and its processing conditions were documented. The optimal coating consisted on a thick inner layer of YSZ coating made by the SPPS process having a thermal conductivity 50% lower than standard YSZ coatings topped with a high temperature tolerant CMAS resistant gadolinium zirconate Coating made by the SPPS process. Noteworthy was the fact that the YSZ to GZO interface made by the SPPS process was not the failure location as had been observed in APS coatings.
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
Evaluations of Advanced Thermal Shock-Resistant Cement (TSRC) Suitable to Withstand Frequent Thermal Cycling (Six-month Report)
This report documents additional evaluations of Thermal Shock-Resistant Cement (TSRC) developed by Brookhaven National Laboratory (BNL). Our work focused on thermal expansion, and fluid flow through the TSRC, and the application of thermal shock to a steel/TSRC sheathed sample. The key contributions of this work to the geothermal community are: 1) Development of a test system to make measurements of material properties at elevated temperature and pressure. 2) Measurements of thermal expansion and permeability of TSRC at elevated temperature and pressure conditions relevant to in situ geothermal conditions. 3) Development of a test system to thermally shock a steel/TSRC sheathed sample at elevated temperature and pressure conditions relevant to in situ geothermal conditions. Herein we report the results of the study of repeated testing upon 3 cylindrical samples supplied by BNL, one steel, one TSRC, and one steel/TSRC sheathed sample.
36 MATERIALS SCIENCE↗
Experimental Investigation of Low Cost, Low Thermal Conductivity Thermal Barrier Coating on HCCI Combustion, Efficiency, and Emissions
In-cylinder surface temperature is of heightened importance for Homogeneous Charge Compression Ignition (HCCI) combustion since the combustion mechanism is thermo-kinetically driven. Thermal Barrier Coatings (TBCs) selectively manipulate the in-cylinder surface temperature, providing an avenue for improving thermal and combustion efficiency. A surface temperature swing during combustion/expansion reduces heat transfer losses, leading to more complete combustion and reduced emissions. At the same time, achieving a highly dynamic response sidesteps preheating of charge during intake and eliminates the volumetric efficiency penalty. The magnitude and temporal profile of the dynamic surface temperature swing is affected by the TBC material properties, thickness, morphology, engine speed, and heat flux from the combustion process. This study follows prior work of authors with Yttria Stabilized Zirconia, which systematically engineered coatings for HCCI combustion. Herein, a modeling study was used to assess the impacts of various TBC material properties, e.g. density, thickness, and thermal conductivity on the temperature swing effect. Reducing conductivity emerged as a most promising avenue, rather than reducing both the density and effective conductivity by increasing porosity, the current work emphasizes a material with natively low conductivity. A novel TBC formulation was developed, leverages a class of materials that, to the author’s best knowledge, have not been used as a thermal barrier coating previously. Here, a systematic experimental investigation was carried out using single-cylinder research engine. Experimental engine studies utilizing the novel ‘glassy’ low-K coating exhibit advanced ignition phasing and reduced combustion duration relative to the baseline engine. Heat transfer measurements indicate a net reduction in heat flux over the entire cycle, although main effect is felt during expansion, and the reduced heat transfer losses manifest in higher gross indicated thermal efficiency by approximately 5-6% on a relative basis.
42 ENGINEERING↗