Engineering topics

Miller, John R.

Publications and source records attributed to Miller, John R..

9 records

DOE OSTI2023

Kinetics and Energetics of Electron Transfer to Dimer Radical Cations

In this work, spectra of the dimer cations naphthalene (Nap 2 •+ ) and ethene (Ethene 2 •+ ) were measured in liquid dichloromethane (DCM). The spectra peak at very different energies, 1.2 and 3.3 eV. In DCM dimerization stabilizes Nap 2 •+ by Δ$G_\text{d}°$(Nap 2 •+ ) = -218 meV relative to the monomer Nap •+ as determined from the dimerization equilibrium constant. Both dimers can transfer a positive charge to hole acceptor molecules, but for both the rate constants rise more gradually with reaction energetics than do many charge transfer reactions previously studied. A striking observation finds that the rate constant for hole transfer from the Nap 2 •+ dimer to phenanthrene is smaller by two decades than that from biphenyl•+ monomer to Nap, although both reactions have the same –Δ$\textit{G}°$=0.05 eV. A plausible interpretation for these observations is the presence of an energy of reorganization, λ(M 2 ), for the dimer that involves movement apart of the two partners in the dimer. While the dimerization equilibrium cannot be measured for Ethene 2 •+ the charge transfer data imply that both Δ$G_\text{d}°$(Ethene 2 •+ ) and λ(Ethene 2 •+ ), are considerably larger, perhaps by factors of 2-4 than for Nap 2 •+ .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Inverted Region in Bimolecular Electron Transfer in Solution Enabled by Delocalization

Rate constants for bimolecular electron transfer (ET) increased with driving force, -ΔG°, reached a plateau, and then decreased in an inverted region. This rate data was described well by electron transfer theory subject to a diffusion-controlled limit. These were for ET from radical anions of polydecylthiophene (P3DT) to a series of acceptors in THF solution. When the donor was the smaller anion of quaterthiophene (T4 •- ) the inverted region was much less prominent, and still less so for when the donor was the anion of bithiophene (T2 •- ). Description of the data using ET theory identifies smaller electronic couplings for the highly-delocalized P3DT anions as enabling the inverted behavior: The presence of a Marcus inverted region is a consequence of delocalized electronic states. The results of this study further imply that electronic couplings smaller than usually found for molecules in contact could boost efficiency of energy storage by electron transfer, and identifies size-mismatch as an important concept in control of electronic couplings.

14 SOLAR ENERGY↗

DOE OSTI2020

Pushing the limits of the electrochemical window with pulse radiolysis in chloroform

Pulse radiolysis (PR) enables the full redox window of a solvent to be accessed, as it does not require electrodes or electrolyte which limit the potentials accessible in voltammetry measurements. PR in chloroform has the additional possibility to enable reaching highly positive potentials because of its large ionization potential (IP). We report PR experiments demonstrated the formation of the (deuterated) chloroform radical cation CDCl 3 + ˙, identifying it as the source of the broad absorption in the visible part of the spectrum. Results indicated that solutes with a redox potential up to +3.7 V vs. Fc/Fc + can be oxidized by CDCl 3 + ˙, which is far beyond what is possible with electrochemical techniques. Oxidation is not efficient because of rapid geminate recombination with chloride counterions, but also due to rapid decomposition of CDCl 3 + ˙ which limits the yield of otherwise longer-lived free ions. The rapid, 6 ± 3 ns, decomposition, confirmed by two independent experiments, means that a solute must be present at a concentration >100 mM to capture >90% of the free holes formed. Addition of ethene removes the broad, overlapping absorptions from ubiquitous (chlorine atom, solute) complexes created by PR in halogenated solvents enabling clear observation of solute cations. The results also unravel the complex radiation chemistry of chloroform including the large reported value G (–CHCl 3 ) = 12 molecules/100 eV for the decomposition of chloroform molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

General Method for Determining Redox Potentials without Electrolyte

A novel method to determine redox potentials without electrolyte is presented here. The method is based on a new ability to determine the dissociation constant, $K°_d$, for ion pairs formed between any radical anion and any inert electrolyte counterion. These dissociation constants can be used to determine relative shifts of redox potential as a function of electrolyte concentration, connecting referenced potentials determined with electrochemistry (with 0.1 M electrolyte) to electrolyte-free values. Pulse radiolysis created radical anions enabling determination of equilibrium constants for electron transfer between anions of donor and acceptor molecules as a function of electrolyte concentration in THF. The measurements determined “composite equilibrium constants”, $K_{eqC}$, which contain information about the dissociation constant for the electrolyte cations, X + , with the radical anions of both the donor, $K°_d$(D –• ,X + ) and the acceptor, $K°_d$(A –• ,X + ). Dissociation constants were obtained for a selection of radical anions with tetrabutylammonium (TBA + ). The electrolyte was found to shift the reduction potentials of small molecules 1-methylpyrene and trans-stilbene by close to +130 mV whereas oligo-fluorenes and polyfluorenes experienced shifts of only (+25 ± 6) mV due to charge delocalization weakening the ion pair. These shifts for reduction of aromatic hydrocarbon molecules are smaller than shifts of +232 and +451 mV seen previously for benzophenone radical anion with TBA + and Na + respectively where the charge on the radical anion is localized largely on one C=O bond, thus forming a more tightly bound ion pair.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2008

Bidirectional Pressure-Regulator System

A bidirectional pressure-regulator system has been devised for use in a regenerative fuel cell system. The bidirectional pressure-regulator acts as a back-pressure regulator as gas flows through the bidirectional pressure-regulator in one direction. Later, the flow of gas goes through the regulator in the opposite direction and the bidirectional pressure-regulator operates as a pressure- reducing pressure regulator. In the regenerative fuel cell system, there are two such bidirectional regulators, one for the hydrogen gas and another for the oxygen gas. The flow of gases goes from the regenerative fuel cell system to the gas storage tanks when energy is being stored, and reverses direction, flowing from the storage tanks to the regenerative fuel cell system when the stored energy is being withdrawn from the regenerative fuel cell system. Having a single bidirectional regulator replaces two unidirectional regulators, plumbing, and multiple valves needed to reverse the flow direction. The term "bidirectional" refers to both the bidirectional nature of the gas flows and capability of each pressure regulator to control the pressure on either its upstream or downstream side, regardless of the direction of flow.

Burke, Kenneth↗

NASA NTRS2007

Integral Radiator and Storage Tank

A simplified, lightweight system for dissipating heat of a regenerative fuel- cell system would include a heat pipe with its evaporator end placed at the heat source and its condenser end integrated into the wall of the regenerative fuel cell system gas-storage tanks. The tank walls act as heat-radiating surfaces for cooling the regenerative fuel cell system. The system was conceived for use in outer space, where radiation is the only physical mechanism available for transferring heat to the environment. The system could also be adapted for use on propellant tanks or other large-surface-area structures to convert them to space heat-radiating structures. Typically for a regenerative fuel cell system, the radiator is separate from the gas-storage tanks. By using each tank s surface as a heat-radiating surface, the need for a separate, potentially massive radiator structure is eliminated. In addition to the mass savings, overall volume is reduced because a more compact packaging scheme is possible. The underlying tank wall structure provides ample support for heat pipes that help to distribute the heat over the entire tank surface. The heat pipes are attached to the outer surface of each gas-storage tank by use of a high-thermal conductance, carbon-fiber composite-material wrap. Through proper choice of the composite layup, it is possible to exploit the high longitudinal conductivity of the carbon fibers (greater than the thermal conductivity of copper) to minimize the unevenness of the temperature distribution over the tank surface, thereby helping to maximize the overall heat-transfer efficiency. In a prototype of the system, the heat pipe and the composite wrap contribute an average mass of 340 g/sq m of radiator area. Lightweight space radiator panels have a mass of about 3,000 g/sq m of radiator area, so this technique saves almost 90 percent of the mass of separate radiator panels. In tests, the modified surface of the tank was found to have an emissivity of 0.85. The composite wrap remained tightly bound to the surface of the tank throughout the testing in thermal vacuum conditions.

Burke, Kenneth A.↗

NASA NTRS2000

BOREAS RSS-19 1994 Seasonal Understory Reflectance Data

The BOREAS RSS-19 team collected airborne remotely sensed images and ground reflectance data for characterizing the radiometric properties of the boreal forest landscape. One objective of BOREAS is to further the understanding of the spectral bidirectional reflectance of typical boreal ecosystem stands in the visible/near-infrared regime. An essential input for any canopy BRDF model is an accurate estimate of the average understory reflectance, both for sunlit and shaded conditions. These variables can be expected to vary seasonally because of species-dependent differences in the phenological cycle of foliar display. In response to these requirements, the average understory reflectance for the flux tower sites of both the NSA (Thompson, Manitoba) and the SSA (Candle Lake, Saskatchewan) was observed throughout the year during five field campaigns. This was done by measuring the nadir reflectance (400 to 850 nm) of sunlit and shaded understory (vegetation and snow cover) along a surveyed LAI transect line (Chen, RSS-07) at each site near solar noon and documenting an average site reflectance. Comparisons between sites reveal differences in the green and infrared regions of the spectra, because of the differing species in the understory for each site. Temporal (seasonal) variation for each site was also observed (06-Feb-1994 to 16-Sep-1994), indicating the changing flora mixtures and changing spectral signatures as the understory matures during the growing season. The data are stored in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884) or from the Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC).

Miller, John R.↗

NASA NTRS1996

NSTAR Ion Thruster and Breadboard Power Processor Functional Integration Test Results

A 2.3 kW Breadboard Power Processing Unit (BBPPU) was developed as part of the NASA Solar Electric Propulsion Technology Application Readiness (NSTAR) Program. The NSTAR program will deliver an electric propulsion system based on a 30 cm xenon ion thruster to the New Millennium (NM) program for use as the primary propulsion system for the initial NM flight. The final development test for the BBPPU, the Functional Integration Test, was carried out to demonstrate all aspects of BBPPU operation with an Engineering Model Thruster. Test objectives included: (1) demonstration and validation of automated thruster start procedures, (2) demonstration of stable closed loop control of the thruster beam current, (3) successful response and recovery to thruster faults, and (4) successful safing of the system during simulated spacecraft faults. These objectives were met over the specified 80-120 VDC input voltage range and 0.5-2.3 output power capability of the BBPPU. Two minor anomalies were noted in discharge and neutralizer keeper current. These anomalies did not affect the stability of the system and were successfully corrected.

Hamley, John A.↗

NASA NTRS1995

Development Status of the NSTAR Ion Propulsion System Power Processor

A 0.5-2.3 kW xenon ion propulsion system is presently being developed under the NASA Solar Electric Propulsion Technology Application Readiness (NSTAR) program. This propulsion system includes a 30 cm diameter xenon ion thruster, a Digital Control Interface Unit, a xenon feed system, and a power processing unit (PPU). The PPU consists of the power supply assemblies which operate the thruster neutralizer, main discharge chamber, and ion optics. Also included are recycle logic and a digital microcontroller. The neutralizer and discharge power supplies employ a dual use configuration which combines the functions of two power supplies into one, significantly simplifying the PPU. Further simplification was realized by implementing a single thruster control loop which regulates the beam current via the discharge current. Continuous throttling is possible over a 0.5-2.3 kW output power range. All three power supplies have been fabricated and tested with resistive loads, and have been combined into a single breadboard unit with the recycle logic and microcontroller. All line and load regulation test results show the power supplies to be within the NSTAR flight PPU specified power output of 1.98 kW. The overall efficiency of the PPU, calculated as the combined efficiencies of the power supplies and controller, at 2.3 kW delivered to resistive loads was 0.90. The component was 6.16 kg. Integration testing of the neutralizer and discharge power supplies with a functional model thruster revealed no issues with discharge ignition or steady state operation.

Hamley, John A.↗