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At least 199 records · Page 11

Flow Effects on the Flammability Diagrams of Solid Fuels

A research program is currently underway with the final objective of developing a fundamental understanding of the controlling mechanisms underlying the flammability diagrams of solid combustible materials and their derived fire properties. Given that there is a high possibility of an accidental fire occurring in a space-based facility, understanding the fire properties of materials that will be used in such facilities is of critical importance. With this purpose, the flammability diagrams of the materials, as those produced by the Lateral Ignition and Flame Spread Test (LIFT) apparatus and by a new forced flow device, the Forced Flow Ignition and Flame Spread Test (FIST) apparatus, will be obtained. The specific objective of the program is to apply the new flammability apparatus, which will more accurately reflect the potential ambient conditions of space-based environments, to the characterization of the materials for space applications. This paper presents a parametric study of oxidizer flow effects on the ignition curve of the flammability diagrams of PMMA. The dependence of the ignition delay time on the external radiant flux and either the sample width (LIFT) or the flow velocity (FIST) has been studied. Although preliminary, the results indicate that natural and forced convection flow changes, affect the characteristics of the ignition curves of the flammability diagrams. The major effect on the ignition time appears to be due to convective transfer variations at the fuel surface. At high radiant fluxes or high flow velocities, however, it appears that gas phase processes become increasingly important, affecting the overall ignition delay time. A numerical analysis of the solid fuel heating and pyrolysis has also been developed. The theoretical predictions approximate the experiments well for conditions in which the gas phase induction time is negligible.

Cordova, J. L.↗

Low-Threshold Visible-to-Ultraviolet Solid-State Triplet-Fusion Upconversion

Visible-to-ultraviolet (UV) triplet-triplet annihilation (TTA) upconversion is an energy-relevant photon-management strategy that converts visible photons into UV photons capable of driving high-energy photochemical processes. Practical implementation requires solid-state thin films, which often require high excitation power. Here, we demonstrate the first solid-state visible-to-UV TTA upconversion thin-film device, using 1,4-bis((tricyclopentylsilyl)ethynyl)naphthalene (TCPS-NAP) as the annihilator and tris(2-phenylpyridine)iridium(III) (Ir(ppy) 3 ) as the sensitizer on silver. Under incoherent 455 nm excitation, the device exhibits blue-to-UV upconversion with a threshold of 4.8 mW/cm 2 . Using surface plasmons in the planar silver film, we achieve green-to-UV upconversion with a 1.11 eV anti-Stokes shift and 6.9 mW/cm 2 threshold, a 12.2 × threshold enhancement over far-field 532 nm excitation. In solution, TCPS-NAP shows excimer-dominated anti-Stokes emission rather than UV upconversion. These results establish a platform for harvesting low-intensity visible light to drive UV processes while demonstrating that solution-phase screening does not predict solid-state upconversion performance.

Luminescence↗

The effect of the London-van der Waals dispersion force on interline heat transfer

A theoretical procedure to determine the heat transfer characteristics of the interline region (junction of liquid-solid-vapor) from the macroscopic optical and thermophysical properties of the system is outlined. The analysis is based on the premise that the interline transport processes are controlled by the London-van der Waals dispersion force between condensed phases (solid and liquid). Numerical values of the dispersion constant are presented. The procedure is used to compare the relative size of the interline heat sink of various systems using a constant heat flux mode. This solution demonstrates the importance of the interline heat flow number, which is evaluated for various systems.

Wayner, P. C., Jr.↗

The effect of the liquid-solid system properties on the interline heat transfer coefficient

A theoretical procedure to determine the heat transfer characteristics of the interline region of an evaporating meniscus using the macroscopic optical and thermophysical properties of the system is outlined. The analysis is based on the premise that the interline transport processes are controlled by the London-van der Waals forces between condensed phases (solid and liquid). The procedure is used to compare the relative size of the interline heat sink of various systems using a constant heat flux model. This solution demonstrates the importance of the interline heat flow number which is evaluated for various systems. The heat transfer characteristics of the decane-steel system are numerically compared with those of the carbon tetrachloride-quartz system.

Wayner, P. C., Jr.↗

X-ray chemical imaging for assessing redox microsites within soils and sediments

Redox reactions underlie several biogeochemical processes and are typically spatiotemporally heterogeneous in soils and sediments. However, redox heterogeneity has yet to be incorporated into mainstream conceptualizations and modeling of soil biogeochemistry. Anoxic microsites, a defining feature of soil redox heterogeneity, are non-majority oxygen depleted zones in otherwise oxic environments. Neglecting to account for anoxic microsites can generate major uncertainties in quantitative assessments of greenhouse gas emissions, C sequestration, as well as nutrient and contaminant cycling at the ecosystem to global scales. However, only a few studies have observed/characterized anoxic microsites in undisturbed soils, primarily, because soil is opaque and microsites require µm-cm scale resolution over cm-m scales. Consequently, our current understanding of microsite characteristics does not support model parameterization. To resolve this knowledge gap, we demonstrate through this proof-of-concept study that X-ray fluorescence (XRF) 2D mapping can reliably detect, quantify, and provide basic redox characterization of anoxic microsites using solid phase “forensic” evidence. First, we tested and developed a systematic data processing approach to eliminate false positive redox microsites, i.e., artefacts, detected from synchrotron-based multiple-energy XRF 2D mapping of Fe (as a proxy of redox-sensitive elements) in Fe-“rich” sediment cores with artificially injected microsites. Then, spatial distribution of Fe II and Fe III species from full, natural soil core slices (over cm-m lengths/widths) were mapped at 1–100 µm resolution. These investigations revealed direct evidence of anoxic microsites in predominantly oxic soils such as from an oak savanna and toeslope soil of a mountainous watershed, where anaerobicity would typically not be expected. We also revealed preferential spatial distribution of redox microsites inside aggregates from oak savanna soils. We anticipate that this approach will advance our understanding of soil biogeochemistry and help resolve “anomalous” occurrences of reduced products in nominally oxic soils.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Material growth and characterization for solid state devices

During the period of this research grant, the process of liquid phase electroepitaxy (LPEE) was used to grow ternary and quaternary alloy III-V semiconductor thin films. Selective area growth of InGaAs was performed on InP substrates using a patterned sputtered quartz or spin-on glass layer. The etch back and growth characteristics with respect to substrate orientation were investigated. The etch back behavior is somewhat different from wet chemical etching with respect to the sidewall profiles which are observed. LPEE was also employed to grow epitaxial layers of InGaAsP alloys on InP substrates. The behavior of Mn as an acceptor dopant was investigated with low temperature Hall coefficient and photoluminescence measurements. A metal-organic vapor phase epitaxy system was partially complete within the grant period. This atmospheric pressure system will be used to deposit III-V compound and alloy semiconductor layers in future research efforts.

Collis, Ward J.↗

The absence of convective stability in incongruent crystal growth on Earth

It is often assumed that convection can be excluded in materials processing by avoiding horizontal temperature gradients, and employing top-heating and horizontal interfaces. Model calculations for vapor transport processes show that this supposition holds only for strictly congruent vapor-solid transitions. This result can be generalized to all fluid-solid phase transitions. Due to the omnipresence of impurity segregation, it is concluded that convective stability is practically unattainable in materials processing on Earth.

Rosenberger, F. E.↗

Influence of Melt Convection on Solid-Liquid Interface Under Terrestrial and Reduced Gravity Environments

Solidification and crystal growth processes involve thermal and solutal gradients within a molten phase. In the presence of gravity, such gradients result in convective flows which interact with diffusion fields at the solid-liquid interface. Dendritic growth kinetics was studied in transparent model systems which freeze similarily to most metals. Succinonitrile shows a strong influence of convection at supercoolings below about 1K. Fluid flows adjacent to solid-liquid interfaces and the behavior of shear flows in vertical annular geometries are studied. Novel low-frequency eigenstates were discovered and classified as coupled modes, for their involvement with interfacial deformation coupled to the fluid flow, and are unknown in systems without deformable interfaces. The dependence of coupled convection modes on interfacial geometry, gravity, fluid properties, and transformation characteristics studied for several annual flow arrangements with nominally pure solid-liquid systems.

Glicksman, M. E.↗

Multiresolution GPC-Structured Control of a Single-Loop Cold-Flow Chemical Looping Testbed

Chemical looping is a near-zero emission process for generating power from coal. It is based on a multi-phase gas-solid flow and has extremely challenging nonlinear, multi-scale dynamics with jumps, producing large dynamic model uncertainty, which renders traditional robust control techniques, such as linear parameter varying H ∞ design, largely inapplicable. This process complexity is addressed in the present work through the temporal and the spatiotemporal multiresolution modeling along with the corresponding model-based control laws. Namely, the nonlinear autoregressive with exogenous input model structure, nonlinear in the wavelet basis, but linear in parameters, is used to identify the dominant temporal chemical looping process dynamics. The control inputs and the wavelet model parameters are calculated by optimizing a quadratic cost function using a gradient descent method. The respective identification and tracking error convergence of the proposed self-tuning identification and control schemes, the latter using the unconstrained generalized predictive control structure, is separately ascertained through the Lyapunov stability theorem. The rate constraint on the control signal in the temporal control law is then imposed and the control topology is augmented by an additional control loop with self-tuning deadbeat controller which uses the spatiotemporal wavelet riser dynamics representation. The novelty of this work is three-fold: (1) developing the self-tuning controller design methodology that consists in embedding the real-time tunable temporal highly nonlinear, but linearly parametrizable, multiresolution system representations into the classical rate-constrained generalized predictive quadratic optimal control structure, (2) augmenting the temporal multiresolution loop by a more complex spatiotemporal multiresolution self-tuning deadbeat control loop, and (3) demonstrating the effectiveness of the proposed methodology in producing fast recursive real-time algorithms for controlling highly uncertain nonlinear multiscale processes. The latter is shown through the data from the implemented temporal and augmented spatiotemporal solutions of a difficult chemical looping cold flow tracking control problem.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Frequency shifting with a solid-state switching capacitor

Frequency shifting, commonly used in electronic signal processing, is applied in tuning, automatic frequency control, antenna element switching, phase shifting, etc. Frequency shifting can be accomplished economically and reliably with simple circuit comprising conventional resistor and solid-state switching device which can be equivalent to two capacitors, depending on switching state.

Mattauch, R. J.↗

Novel Superionic Na Conductors for Solid‐State Na batteries: Materials and Interface

This project aims to advance the fundamental understanding on how the cation or anion doping influence on the crystal structure, phase stability and ion transport of novel Na superionic conductors. Specifically, we focus on the Na 3-x A x SbS 4-y X y family solid electrolytes (A: cation dopant, X: anion dopant), a class of promising materials for all-solid-state sodium batteries owing to their high ionic conductivity and compositional tunability. By integrating materials synthesis, neutron scattering, and electrochemical characterization and theoretical simulations, this project sees to elucidate 1) how does the synthesis approaches (solid-state reaction, low-temperature reaction) on the phase purity and doping process; 2) how chemical doping (A: cation dopants such as Sn; X: anion dopants such as Se, F) modulate lattice dynamics and Na+ migration as well as interface stability toward Na metal. Specifically, this project’s proposed technology involves three objectives: (1) synthesize novel Na-ion conductors (anion or cation doped Na 3 SbS 4 ) with high phase purity and examine their structural features (e.g., phase stability); (2) understand Na-ion conductive properties of new Na-ion conductors through a combination of experimental characterizations and theoretical simulations; (3) investigate the interface stability of novel Na superionic conductors with electrode materials in solid-state Na batteries. These objectives will be achieved through combined experimental synthesis/characterizations and computational approaches. The obtained knowledge will provide a comprehensive synthesis-structure-property correlation, enabling the rational design of novel solid-state conductors with excellent conductivity and stability.

25 ENERGY STORAGE↗

Chemical Compensation Challenges in Processing Antiferroelectric PbZrO 3 Thin Films

The electric field-induced antipolar-to-polar phase transition in antiferroelectric materials is accompanied by large changes in the structural and functional response, making them attractive for many applications ranging from pulsed energy capacitors to high-strain-high (blocking-)force actuators, solid-state heating and cooling systems, and optoelectronic devices. PbZrO 3 , as an end member of the PZT, (x)PbZr 1–x Ti x O 3 , solid solution, has been the subject of many studies. However, processing of perovskite PbZrO 3 is extremely challenging due to phase instabilities induced by Pb loss at the temperatures necessary for perovskite crystallization. Here, we discuss the challenges associated with Pb loss, as well as its compensation through bulk Pb overstoichiometry and interfacial PbO additions, in chemical solution processed, highly oriented PbZrO 3 thin films. For both 042 o - and 001 o -oriented (o-orthorhombic distortion) PbZrO 3 thin films, the crystallization interfaces are the most important contributors to Pb loss and off-stoichiometric outcomes, and no single approach was sufficient to address these challenges. Pb-rich and Pb-deficient nonperovskite phases including ZrO x were only observable through microscopic characterization, and X-ray diffraction alone could not rule out the presence of such secondary phases. “Ideal” macroscopic antiferroelectric polarization-electric field double hysteresis curves were observed despite (at times) the large presence of secondary phases. However, reduced saturation polarization and increased phase transition electric fields were observed concomitantly with the presence of secondary phase(s) and tentatively assigned to the voltage drop across the ZrO x nanocrystals. Based on these results, it is imperative that the presence of secondary phases always be addressed (beyond X-ray diffraction spectra) in order to correctly evaluate the properties of antiferroelectric films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solid state photochemistry of polycarbonates

The quantum yield of photoFries rearrangement in a polycarbonate film has been analyzed as a function of temperature and humidity on the basis of previously reported (Koyler and Mann, 1977) experimental data. Results indicate that in the homogeneous amorphous phase, photoFries rearrangement is a concerted process proceeding either from the pi star reversed arrow n singlet, in which case it must be subject to considerable self quenching, or from a triplet, presumably the first triplet since the lifetime of higher triplets is expected to be very short in the solid phase. If the parent excited state is the first triplet, chain scission is possibly an independent process, probably occurring from the pi star reversed arrow n singlet. Evidence of chain scission on photodegradation in the solid state includes loss of C-O and C-C bond intensities revealed in the Fourier transform infrared spectra, gel permeation chromotography elution profiles of degraded film samples dissolved in CHCl3, and a decrease in tensile strength and T sub g as photodegradation proceeds. Chain scission is apparently inhibited as photoFries products accumulate.

Gupta, A.↗

A Review of Modeling Approaches for Predicting Frost Growth and Defrosting on Tube-Fin Heat Exchangers: Preprint

Frost formation and growth on the evaporator surface is a common process that deteriorates the air-refrigerant heat transfer and restricts airflow. This degrades the performance of the vapor compression system by increasing temperature lift and air-side pressure drop. To accurately predict these effects during coil frosting, as well as the energy use and duration of the defrost process, there is a need to estimate the heat and mass transfer, momentum transport, and solid-liquid and liquid-vapor phase change. Therefore, in the past few decades, continuous effort has been made to model frosting and defrosting processes using approaches ranging from empirical correlations to computational fluid dynamic models. To provide a clearer overview for researchers, engineers, and manufacturers in this field, this paper provides a comprehensive literature review for frosting and defrosting models. The paper begins with theoretical background of frost formation and defrost processes, and then reviews the common modeling approaches in literature and their underlying assumptions when trying to account for various physical phenomenon. Based on the literature review, the most critical modeling effort for frost formation is the determination of frost densification rate and frost growth rate. Various methods to predict these two parameters are reviewed. Empirical correlations commonly used for frost density and thermal conductivity are presented and compared. For the defrost process, various multi-stage models have been proposed with different assumptions. Some assume the presence of air gap between the tube wall and the frost, while others consider the melted frost flow due to gravity. We also review physics-based and empirical approaches to integrate defrost models into heat pump models. We conclude by identifying research gaps and providing recommendations.

defrost↗

Distinct Melt Infusion Architectures of Antiperovskite Solid Electrolytes

Antiperovskite solid electrolytes are an emerging class of lithium‐ion conductors distinguished by their unusually low melting points, enabling scalable, low‐temperature processing routes not accessible to most solid electrolytes. In this work, we synthesize phase‐pure chloride (Cl), bromide (Br), and mixed halide (ClBr) variants of antiperovskites and investigate their ionic conductivities in both powder and hot‐pressed forms. Hot pressing significantly enhances conductivity across all compositions, while energy‐dispersive X‐ray spectroscopy (EDS) of the mixed halide system reveals halide surface migration during densification. We further investigate the melt‐infiltration behavior of these electrolytes into substrates relevant to solid‐state battery architectures, including Al and Cu current collectors, conventional NMC and LFP cathodes, and a foamed NMC cathode with a highly porous architecture. The foamed cathode enables deep and uniform electrolyte penetration, highlighting the role of electrode architecture in facilitating melt infiltration. Across all substrates, electrolyte halide chemistry strongly influences wetting behavior, penetration depth, and resulting microstructural morphology. Together, these results establish clear processing–structure relationships for melt‐infiltrated antiperovskite solid electrolytes and demonstrate how electrolyte chemistry and electrode architecture govern interfacial morphology during integration, providing practical guidelines for processing and structural design in solid‐state battery systems.

antiperovskite↗

Creep deformation of B2 aluminides

The creep resistance and elevated temperature deformation mechanisms in CoAl, FeAl, and NiAl are reviewed. The stress and temperature dependencies of the steady state creep rate, the primary creep behavior, the dislocation substructure, and the response during transient tests are used as the main indicators of the deformation processes. In single phase intermetallics, the influence of grain size, stoichiometry, and solid solution hardening have been examined. In addition, the effect of adding dispersoids, precipitates, and other types of reinforcements to improve creep strength are compared.

Nathal, M. V.↗

Preparation Of Strong, Dense Potassium Beta''-Alumina Ceramic

Improved process for making mechanically strong, dense, phase-pure potassium beta''-alumina solid electrolyte (K-BASE) results in material superior to all previous K-BASE preparations and similar to commercial Na-BASE in strength, phase purity and high-temperature ionic conductivity. Potassium-based alkali-metal thermal-to-electric conversion (AMTEC) cells expected to operate efficiently at lower heat-input temperatures and lower rejection temperatures than sodium-based AMTEC cells, making them appropriate for somewhat different applications.

Williams, Roger M.↗

A Noncontact Measurement Technique for the Density and Thermal Expansion Coefficient of Solid and Liquid Materials

A noncontact measurement technique for the density and the thermal expansion refractory materials in their molten as well as solid phases is presented. This technique is based on the video image processing of a levitated sample. Experiments were performed using the high-temperature electrostatic levitator (HTESL) at the Jet Propulsion Laboratory in which 2-3 mm diameter samples can be levitated, melted, and radiatively cooled in a vacuum. Due to the axisymmetric nature of the molten samples when levitated in the HTESL, a rather simple digital image analysis can be employed to accurately measure the volumetric change as a function of temperature. Density and the thermal expansion coefficient measurements were made on a pure nickel sample to test the accuracy of the technique in the temperature range of 1045-1565 C. The result for the liquid phase density can be expressed by p = 8.848 + (6.730 x 10(exp -4)) x T (degC) g/cu cm within 0.8% accuracy, and the corresponding thermal expansion coefficient can be expressed by Beta=(9.419 x 10(exp -5)) - (7.165 x 10(exp -9) x T (degC)/K within 0.2% accuracy.

Chung, Sang K.↗