Multimode-Optical-Fiber Imaging Probe
This work describes an approach for recovering images from tightly confined spaces using multimode.
phase↗
SEARCH · Engineering Papers
Results for “conjugate spaces”
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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Electrochemical Capacitance Traces with Interlayer Spacing in Two‐dimensional Conductive Metal–Organic Frameworks
Abstract Electrically conductive metal–organic frameworks (MOFs) are promising candidates for electrochemical capacitors (EC) for fast energy storage due to their high specific surface areas and potential for redox activity. To maximize energy density, traditional inorganic pseudocapacitors have utilized faradaic processes in addition to double‐layer capacitance. Although conductive MOFs are usually comprised of redox active ligands which allow faradaic reactions upon electrochemical polarization, systematic studies providing deeper understanding of the charge storage processes and structure‐function relationships have been scarce. Here, we investigate the charge storage mechanisms of a series of triazatruxene‐based 2D layered conductive MOFs with variable alkyl functional groups, Ni 3 (HIR 3 ‐TAT) 2 (TAT=triazatruxene; R=H, Et, n ‐Bu, n ‐Pent). Functionalization of the triazatruxene core allows for systematic variation of structural parameters while maintaining in‐plane conjugation between ligands and metals. Specifically, R groups modulate interlayer spacing, which in turn shifts the charge storage mechanism from double‐layer capacitance towards pseudocapacitance, leading to an increase in molar specific capacitance from Ni 3 (HIH 3 ‐TAT) 2 to Ni 3 (HIBu 3 ‐TAT) 2 . Partial exfoliation of Ni 3 (HIBu 3 ‐TAT) 2 renders redox active ligand moieties more accessible, and thus increases the dominance of faradaic processes. Our strategy of controlling charge storage mechanism through tuning the accessibility of redox‐active sites may motivate further design and engineering of electrode materials for EC.
Su, Alice Y.↗
Electrochemical Capacitance Traces with Interlayer Spacing in Two‐dimensional Conductive Metal–Organic Frameworks
Abstract Electrically conductive metal–organic frameworks (MOFs) are promising candidates for electrochemical capacitors (EC) for fast energy storage due to their high specific surface areas and potential for redox activity. To maximize energy density, traditional inorganic pseudocapacitors have utilized faradaic processes in addition to double‐layer capacitance. Although conductive MOFs are usually comprised of redox active ligands which allow faradaic reactions upon electrochemical polarization, systematic studies providing deeper understanding of the charge storage processes and structure‐function relationships have been scarce. Here, we investigate the charge storage mechanisms of a series of triazatruxene‐based 2D layered conductive MOFs with variable alkyl functional groups, Ni 3 (HIR 3 ‐TAT) 2 (TAT=triazatruxene; R=H, Et, n ‐Bu, n ‐Pent). Functionalization of the triazatruxene core allows for systematic variation of structural parameters while maintaining in‐plane conjugation between ligands and metals. Specifically, R groups modulate interlayer spacing, which in turn shifts the charge storage mechanism from double‐layer capacitance towards pseudocapacitance, leading to an increase in molar specific capacitance from Ni 3 (HIH 3 ‐TAT) 2 to Ni 3 (HIBu 3 ‐TAT) 2 . Partial exfoliation of Ni 3 (HIBu 3 ‐TAT) 2 renders redox active ligand moieties more accessible, and thus increases the dominance of faradaic processes. Our strategy of controlling charge storage mechanism through tuning the accessibility of redox‐active sites may motivate further design and engineering of electrode materials for EC.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Tuning Transport via Interaction Strength in Cationic Conjugated Polyelectrolytes
Tuning polymer-ion interaction strength is critical for balancing ion solvation and transport in solid polymer electrolytes for battery applications. In mixed Li + /electron conducting systems for improved battery binders, the design space is further complicated by seemingly opposing design rules for electron and ion conducting polymers. Conjugated polymers functionalized with cationic side chains have demonstrated high ionic conductivity, lithium transport, and electronic conductivity by combining long-range polymer ordering with diffuse ion interactions. Herein, we demonstrate a family of mixed conducting polythiophenes functionalized with a range of cationic side chains, namely imidazolium, trimethylammonium, and ammonium groups. The strength of ionic interactions and structure of the side chains govern lithium-selective transport, resulting in high Li + conductivity (~10 –4 S/cm at 80 °C) and electronic conductivity. The more diffuse imidazolium ion affords labile ionic interactions, resulting in higher lithium transference than the other cations studied. Electronic conductivity is also higher in the imidazolium system, stemming from the ability of the planar side chains to stack while also accommodating the bulky TFSI – counterions. Finally, these results demonstrate the importance of interaction strength in ion transport while also indicating that the physical structure of the side chain has an impact on electronic conduction. The imidazolium group strikes a balance, achieving superior properties across all metrics.
36 MATERIALS SCIENCE↗
An investigation of wave-particle interactions and particle dynamics using electron beams injected from sounding rockets
Electrons with energy up to 40 kV have been injected into semi-trapped orbits from sounding rockets at Wallops Island, Virginia, and at Fort Churchill, Manitoba, Canada. By directing the rocket trajectory to have a horizontal component which in direction and speed matched the bounce displacement of the injected electrons, it was possible to detect conjugate echoes at Wallops and possibly at Churchill, and to study the distribution of the echoes in space, time and energy. By combining observations of many echoes, a composite picture can be obtained of the beam patterns. Atmospheric scattering at the conjugate point of Wallops Island has been extensively studied, and the process produces a scale width of 5-10 m, but with an echo intensity which is only 10% of theoretical estimates.
Winckler, J. R.↗
Manipulating Photoconduction in Cu–Pyrene 1-D Coordination Nanosheets by Modulating Interlayer π–π Stacking
2D conductive metal organic frameworks (MOFs) have become promising candidates for applications in electronic and photoelectronic devices. However, the lack of a fundamental understanding of the charge transport mechanism and synthetic design to alter their conductivity limits their potential applications. In this work, we report the design and synthesis of two 1D Cu–pyrene coordination nanosheets, Cu–pyrene-4,5,9,10 tetrathiol (Cu-PTT) and Cu–2,7-di-tert-butylpyrene-4,5,9,10-tetrathiol (Cu– tBu PTT), as models of 2D conductive MOFs, where the introduction of two different functional groups (H and tert-butyl groups) at the 2 and 7 positions of the PTT ligands is used to tune the interlayer distance and π–π stacking of MOFs. Using optical pump terahertz probe spectroscopy, we show that both nanosheets exhibit appreciable photoconduction, but the photoconduction in Cu– tBu PTT is reduced with respect to that in Cu–PTT, which can be attributed to the larger interlayer distance in the former leading to the decoupling of the interlayer charge transport pathway. Furthermore, these results demonstrate a unique strategy to investigate the impact of out-of-plane extended conjugation on photoconduction in conductive conjugated polymers, MOFs, or coordination nanosheets through adjusting their interlayer spacing.
14 SOLAR ENERGY↗
Conjugated polyelectrolyte-based ternary exciton funnels via liposome scaffolds
There is great interest in developing inexpensive, molecular light-harvesting systems capable of efficiently converting photon energy to chemical potential energy. It is highly desirable to do so using self-assembly and in a manner that supports environmentally benign processing. A critical consideration in any such assembly is the ability to absorb a substantial fraction of the solar emission spectrum and to be able to efficiently move excited states through the space to a functional interface. We have previously shown that aqueous inter-conjugated polyelectrolyte (CPE) complexes can act as ultrafast and efficient energy-transfer antennae. Here we demonstrate formation of a hierarchically assembled, aqueous system based on an inter-CPE exciton donor/acceptor network and a lipid vesicle scaffold. Using a model small-molecule organic semiconductor embedded in the vesicle membrane, we form a ternary exciton funnel that is oriented towards the membrane interior. We show that, although energy transfer is efficient, the assembly morphology depends sensitively on preparation conditions and relative ionic stoichiometry. We propose several approaches towards stabilizing such aqueous assemblies. Furthermore, this work highlights a path to formation of an aqueous, panchromatic light-harvesting system, whose functional complexity can be systematically increased with modularity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Electric Field Conjugation in the Presence of Model Uncertainty
The Wide-Field Infrared Survey Telescope (WFIRST) is a 2.4-meter-diameter space telescope NASA program. The payload will include a coronagraph instrument (CGI). The CGI designs under development use deformable mirrors (DM) to create a point spread function (PSF) with a dark region around the obscured star object. Electric field conjugation (EFC) is an iterative nonlinear optimization procedure that uses measurements of the electric field at the image to determine the DM displacements to modify the PSF to create the region of high contrast in the image. EFC requires a numerical model of the coronagraph to calculate the Jacobian of the system, which is used, along with regularization, to solve for the DM displacements for each iteration of the nonlinear optimization. Ideally, the coronagraph is aligned and calibrated, and the calibration data are used in the numerical model for calculating the Jacobian. However, calibration and alignment measurements always contain uncertainty resulting in calibration error. Therefore, the Jacobian calculated from the numerical model is not an exact representation of the physical coronagraph, and the resulting DM solution for an EFC iteration does not have the exact impact on the electric field of the coronagraph as predicted by the EFC. The result is slow convergence, and, as will be shown, drives the use of more restrictive regularization. Using Monte Carlo trials, we investigate the effect of calibration error on EFC convergence and regulatization. Comparison to results from the High Contrast Imaging Testbed Hybrid Lyot Coronagraph are also presented.
Marx, David↗
On the electromagnetic scattering from infinite rectangular grids with finite conductivity
A variety of methods can be used in constructing solutions to the problem of mesh scattering. However, each of these methods has certain drawbacks. The present paper is concerned with a new technique which is valid for all spacings. The new method involved, called the fast Fourier transform-conjugate gradient method (FFT-CGM), represents an iterative technique which employs the conjugate gradient method to improve upon each iterate, utilizing the fast Fourier transform. The FFT-CGM method provides a new accurate model which can be extended and applied to the more difficult problems of woven mesh surfaces. The formulation of the FFT-conjugate gradient method for aperture fields and current densities for a planar periodic structure is considered along with singular operators, the formulation of the FFT-CG method for thin wires with finite conductivity, and reflection coefficients.
Christodoulou, C. G.↗
Cobalt‐Catalyzed Electroreductive Alkylation of Unactivated Alkyl Chlorides with Conjugated Olefins
Abstract Reactions of unactivated alkyl chlorides under mild and sustainable conditions are rare compared to those of alkyl bromides or iodides. As a result, synthetic methods capable of modifying the vast chemical space of chloroalkane reagents, wastes, and materials are limited. We report the cobalt‐catalyzed reductive addition of unactivated alkyl chlorides to conjugated alkenes. Co‐catalyzed activation of alkyl chlorides is performed under electroreductive conditions, and the resulting reactions constitute formal alkyl‐alkyl bond formation. In addition to developing an operationally simple methodology, detailed mechanistic studies provide insights into the elementary steps of a proposed catalytic cycle. In particular, we propose a switch in the mechanism of C−Cl bond activation from nucleophilic substitution to halogen atom abstraction, which is critical for efficiently generating alkyl radicals. These mechanistic insights were leveraged in designing ligands that enable couplings of primary, secondary, and tertiary alkyl chlorides.
Al Zubaydi, Samir↗
Cobalt‐Catalyzed Electroreductive Alkylation of Unactivated Alkyl Chlorides with Conjugated Olefins
Abstract Reactions of unactivated alkyl chlorides under mild and sustainable conditions are rare compared to those of alkyl bromides or iodides. As a result, synthetic methods capable of modifying the vast chemical space of chloroalkane reagents, wastes, and materials are limited. We report the cobalt‐catalyzed reductive addition of unactivated alkyl chlorides to conjugated alkenes. Co‐catalyzed activation of alkyl chlorides is performed under electroreductive conditions, and the resulting reactions constitute formal alkyl‐alkyl bond formation. In addition to developing an operationally simple methodology, detailed mechanistic studies provide insights into the elementary steps of a proposed catalytic cycle. In particular, we propose a switch in the mechanism of C−Cl bond activation from nucleophilic substitution to halogen atom abstraction, which is critical for efficiently generating alkyl radicals. These mechanistic insights were leveraged in designing ligands that enable couplings of primary, secondary, and tertiary alkyl chlorides.
Al Zubaydi, Samir↗
Phase-Conjugate Receiver for Gaussian-State Quantum Illumination
An active optical sensor probes a region of free space that is engulfed in bright thermal noise to determine the presence (or absence) of a weakly reflecting target. The returned light (which is just thermal noise if no target is present, and thermal noise plus a weak reflection of the probe beam if a target is present) is measured and processed by a receiver and a decision is made on whether a target is present. It has been shown that generating an entangled pair of photons (which is a highly nonclassical state of light), using one photon as the probe beam and storing the other photon for comparison to the returned light, has superior performance to the traditional classical-light (coherent-state) target detection sensors. An entangled-photon transmitter and optimal receiver combination can yield up to a factor of 4 (i.e., 6 dB) gain in the error-probability exponent over a coherent state transmitter and optimal receiver combination, in a highly lossy and noisy scenario (when both sensors have the same number of transmitted photons). However, the receiver that achieves this advantage is not known. One structured receiver can close half of the 6-dB gap (i.e., a 3-dB improvement). It is based on phase-conjugating the returned light, then performing dual-balanced difference detection with the stored half of the entangled-photon pair. Active optical sensors are of tremendous value to NASA s missions. Although this work focuses on target detection, it can be extended to imaging (2D, 3D, hyperspectral, etc.) scenarios as well, where the image quality can be better than that offered by traditional active sensors. Although the current work is theoretical, NASA s future missions could benefit significantly from developing and demonstrating this capability. This is an optical receiver design whose components are, in principle, all implementable. However, the work is currently entirely theoretical. It is necessary to: 1. Demonstrate a bench-top proof of the theoretical principle, 2. Create an operational prototype off-the-bench, and 3. Build a practical sensor that can fly in a mission.
Erkmen, Baris I.↗
Magnetic Ordering in a High‐Spin Donor–Acceptor Conjugated Polymer
Abstract The development of open‐shell organic molecules that magnetically order at room temperature,which can be practically applied, remains a grand challenge in chemistry, physics, and materials science. Despite the exploration of vast chemical space, design paradigms for organic paramagnetic centers generally result in unpaired electron spins that are unstable or isotropic. Here, a high‐spin conjugated polymer is demonstrated, which is composed of alternating cyclopentadithiophene and benzo[1,2‐ c ;4,5‐ c ′]bis[1,2,5]thiadiazole heterocycles, in which macromolecular structure and topology coalesce to promote the spin center generation and intermolecular exchange coupling. Electron paramagnetic resonance (EPR) spectroscopy is consistent with spatially localized spins, while magnetic susceptibility measurements show clear anisotropic spin ordering and exchange interactions that persist at room temperature. The application of long‐range π‐correlations for spin center generation promotes remarkable stability. This work offers a fundamentally new approach to the implementation of this long‐sought‐after physical phenomenon within organic materials and the integration of manifold properties within emerging technologies.
Steelman, Michael E.↗
The development of the Poincare-similar elements with eccentric anomaly as the independent variable
A new set of element differential equations for the perturbed two-body motion is derived. The elements are canonical and are similar to the classical canonical Poincare elements, which have time as the independent variable. The phase space is extended by introducing the total energy and time as canonically conjugated variables. The new independent variable is, to within an additive constant, the eccentric anomaly. These elements are compared to the Kustaanheimo-Stiefel (KS) element differential equations, which also have the eccentric anomaly as the independent variable. For several numerical examples, the accuracy and stability of the new set are equal to those of the KS solution. This comparable accuracy result can probably be attributed to the fact that both sets have the same time element and very similar energy elements. The new set has only 8 elements, compared to 10 elements for the KS set. Both sets are free from singularities due to vanishing eccentricity and inclination.
Bond, V. R.↗
Sub-domain decomposition methods and computational controls for multibody dynamical systems
This paper presents a concurrent methodology to simulate the dynamics of flexible multibody systems with a large number of degrees of freedom. A general class of open-loop structures is treated and a redundant coordinate formulation is adopted. A range space method is used in which the constraint forces are calculated using a preconditioned conjugate gradient method. By using a preconditioner motivated by the regular ordering of the directed graph of the structures, it is shown that the method is order N in the total number of coordinates of the system. The overall formulation has the advantage that it permits fine parallelization and does not rely on system topology to induce concurrency. It can be efficiently implemented on the present generation of parallel computers with a large number of processors. Validation of the method is presented via numerical simulations of space structures incorporating large number of flexible degrees of freedom.
Menon, R. G.↗
Excited state dynamics of cis,cis-1,3-cyclooctadiene: Non-adiabatic trajectory surface hopping
We have performed trajectory surface hopping dynamics for cis,cis-1,3-cyclooctadiene to investigate the photochemical pathways involved after being excited to the S 1 state. Our calculations reveal ultrafast decay to the ground state, facilitated by conical intersections involving distortions around the double bonds. The main distortions are localized on one double bond, involving twisting and pyramidalization of one of the carbons of that double bond (similar to ethylene), while a limited number of trajectories decay via delocalized (non-local) twisting of both double bonds. The interplay between local and non-local distortions is important in our understanding of photoisomerization in conjugated systems. The calculations show that a broad range of the conical intersection seam space is accessed during the non-adiabatic events. Several products formed on the ground state have also been observed.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Numerical Modeling of the Chilldown of Cryogenic Transfer Lines Using a Sinda/GFSSP Integrated Solver
An important first step in cryogenic propellant loading is the chilldown of transfer lines. During the chilldown of the transfer line, the flow is two-phase and unsteady, with solid to fluid heat transfer and therefore a coupled thermo-fluid analysis is necessary to model the system. This paper describes a numerical model of pipe chilldown that utilizes the Sinda/GFSSP Conjugate Integrator (SGCI). SGCI is a new analysis tool developed at NASA's Marshall Space Flight Center (MSFC). SGCI facilitates the solution of thermofluid problems in interconnected solid-fluid systems. The solid component of the system is modeled in MSC Patran and translated into an MSC Sinda thermal network model. The fluid component is modeled in GFSSP, the Generalized Fluid System Simulation Program. GFSSP is a general network flow solver developed at NASA/MSFC. GFSSP uses a finite-volume approach to model fluid systems that can include phase change, multiple species, fluid transients, and heat transfer to simple solid networks. SGCI combines the GFSSP Fortran code with the Sinda input file and compiles the integrated model. Sinda solves for the temperatures of the solid network, while GFSSP simultaneously solves the fluid network for pressure, temperature, and flow rate. The two networks are coupled by convection heat transfer from the solid wall to the cryogenic fluid. The model presented here is based on a series of experiments conducted in 1966 by the National Bureau of Standards (NBS). A vacuum-jacketed, 200 ft copper transfer line was chilled by liquid nitrogen and liquid hydrogen. The predictions of transient temperature profiles and chilldown time of the integrated Sinda/GFSSP model will be compared to the experimental measurements.
LeClair, Andre↗
On the Development of the Marshall Grazing Incidence X-ray Spectrograph (MaGIXS) Mirrors
The Marshall Grazing Incidence X-ray Spectrograph (MaGIXS) is a sounding rocket experiment that will obtain spatially resolved soft X-ray spectra of the solar corona from 0.5 - 2 keV. The optical system comprises a Wolter-I telescope mirror, a slit spectrograph, and a CCD camera. The spectrograph has a finite conjugate paraboloid pair, which re-images the slit, and a varied line-space planar reflection grating. Both the Wolter-I mirror and paraboloid pair are being fabricated at the NASA Marshall Space Flight Center (MSFC), using nickel replication. The MaGIXS mirror mandrels have been diamond turned, polished, and have yielded a set of engineering mirrors. Unlike other grazing incidence instruments, such as FOXSI, ART-XC, and IXPE, the MaGIXS prescriptions have large departure from a cone. This property exacerbates challenges with conventional lap polishing techniques and interferometric metrology. Here we discuss the progression of the optical surfaces of the mandrels through lap polishing, X-ray data from the replicated shells obtained in the MSFC Stray Light Facility (SLF), and our transition to using the ZEEKO computer numerical controlled (CNC) polisher for figure correction.
Champey, Patrick↗