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Elucidation of Free Radical and Optogalvanic Spectroscopy Associated with Microgravity Combustion via Conventional and Novel Laser Platforms

Combustion studies under both normal gravity and microgravity conditions depend a great deal on the availability and quality of the diagnostic systems used for such investigations. Microgravity phenomena are specially susceptible to even small perturbations and therefore non-intrusive diagnostic techniques are of paramount importance for successful understanding of reduced-gravity combustion phenomena. Several non-intrusive diagnostic techniques are available for probing and delineating normal as well as reduced gravity combustion processes, such as Rayleigh scattering, Raman scattering, Mie scattering, velocimetry, interferometric and Schlieren techniques, emission and laser-induced fluorescence (LIF) spectroscopy. Our approach is to use the LIF technique as a non-intrusive diagnostic tool for the study of combustion-associated free radicals and use the concomitant optogalvanic transitions to accomplish precise calibration of the laser wavelengths used for recording the excitation spectra of transient molecular species. In attempting to perform spectroscopic measurements on chemical intermediates, we have used conventional laser sources as well as new and novel platforms employing rare-earth doped solid-state lasers. Conventional (commercially available) sources of tunable UV laser radiation are extremely cumbersome and energy-consuming devices that are not very suitable for either in-space or in-flight (or microgravity drop tower) experiments. Traditional LIF sources of tunable UV laser radiation involve in addition to a pump laser (usually a Nd:YAG laser with an attached frequency-doubling stage), a tunable dye laser. In turn, the dye laser has to be provided with a dye circulation system and a subsequent stage for frequency-doubling of the dye laser radiation, together with a servo-tuning system (termed the 'Autotracker') to follow the wavelength changes and also an optical system (called the 'Frequency Separator') for separation of the emanating visible and UV beams. In contrast to this approach, we have devised an alternate arrangement for recording LIF excitation spectra of free radicals (following appropriate precursor fragmentation) that utilizes a tunable rare-earth doped solid state laser system with direct UV pumping. We have designed a compact and portable tunable UV laser system incorporating features necessary for both in-space and in-flight spectroscopy experiments. For the purpose of LIF excitation, we have developed an all-solid-state tunable UV laser that employs direct pumping of the solid-state UV-active medium employing UV harmonics from a Nd:YAG laser. An optical scheme with counterpropagating photolysis and excitation beams focused by suitable lenses into a reaction vacuum chamber was employed.

Misra, Prabhakar↗

Inelastic electron tunneling spectroscopy

Inelastic electron tunneling spectroscopy is a useful technique for the study of vibrational modes of molecules adsorbed on the surface of oxide layers in a metal-insulator-metal tunnel junction. The technique involves studying the effects of adsorbed molecules on the tunneling spectrum of such junctions. The data give useful information about the structure, bonding, and orientation of adsorbed molecules. One of the major advantages of inelastic electron tunneling spectroscopy is its sensitivity. It is capable of detecting on the order of 10 to the 10th molecules (a fraction of a monolayer) on a 1 sq mm junction. It has been successfully used in studies of catalysis, biology, trace impurity detection, and electronic excitations. Because of its high sensitivity, this technique shows great promise in the area of solid-state electronic chemical sensing.

Khanna, S. K.↗

High Resolution, Non-Dispersive X-Ray Calorimeter Spectrometers on EBITs and Orbiting Observatories

X-ray spectroscopy is the primary tool for performing atomic physics with Electron beam ion trap (EBITs). X-ray instruments have generally fallen into two general categories, 1) dispersive instruments with very high spectral resolving powers but limited spectral range, limited count rates, and require an entrance slit, generally, for EBITs, defined by the electron beam itself, and 2) non-dispersive solid-state detectors with much lower spectral resolving powers but that have a broad dynamic range, high count rate ability and do not require a slit. Both of these approaches have compromises that limit the type and efficiency of measurements that can be performed. In 1984 NASA initiated a program to produce a non-dispersive instrument with high spectral resolving power for x-ray astrophysics based on the cryogenic x-ray calorimeter. This program produced the XRS non-dispersive spectrometers on the Astro-E, Astro-E2 (Suzaku) orbiting observatories, the SXS instrument on the Astro-H observatory, and the planned XMS instrument on the International X-ray Observatory. Complimenting these spaceflight programs, a permanent high-resolution x-ray calorimeter spectrometer, the XRS/EBIT, was installed on the LLNL EBIT in 2000. This unique instrument was upgraded to a spectral resolving power of 1000 at 6 keV in 2003 and replaced by a nearly autonomous production-class spectrometer, the EBIT Calorimeter Spectrometer (ECS), in 2007. The ECS spectrometer has a simultaneous bandpass from 0.07 to over 100 keV with a spectral resolving power of 1300 at 6 keV with unit quantum efficiency, and 1900 at 60 keV with a quantum efficiency of 30%. X-ray calorimeters are event based, single photon spectrometers with event time tagging to better than 10 us. We are currently developing a follow-on instrument based on a newer generation of x-ray calorimeters with a spectral resolving power of 3000 at 6 keV, and improved timing and measurement cadence. The unique capabilities of the x-ray calorimeter spectrometer, coupled with higher spectral resolution dispersive spectrometers to resolve line blends, has enabled many science investigations, to date mostly in our x-ray laboratory astrophysics program. These include measurements of absolute cross sections for Land K shell emission from Fe and Ni, charge exchange measurements in many astrophysically abundant elements, lifetime measurements, line ratios, and wavelength measurements. In addition, we have performed many additional measurements in nuclear physics, and in support of diagnostics for laser fusion, for example. In this presentation we will give a detailed overview of x-ray calorimeter instruments in general and in our EBIT laboratory astrophysics program in particular. We will also discuss the science yield of our measurements at EBIT over the last decade) prospects for future science enabled by the current generation of spectrometers and that will be expanded in the near future by the next generation of spectrometers starting in 2611.

Porter, Frederick S.↗

Thermochemical Stability of Ca2Yb8(SiO4)6O2 Apatite in Presence of Molten Calcium-Magnesium-Aluminosilicate (CMAS)

Thermochemical stability of ytterbium silicon oxyapatite Ca 2 Yb 8 (SiO 4 ) 6 O 2 (CYbS) in the presence of molten calcium-magnesium aluminosilicate (CMAS) has been investigated at elevated temperatures for consideration as a thermal and environmental barrier coating (T/EBC) material. CYbS apatite powder was synthesized from the constituent oxides via a solid-state reaction method. Hot-pressed apatite substrates were exposed to molten CMAS at 1200, 1300, and 1400 °C for 1, 10, and 50 h. Development of phases in the interaction region of the heat-treated specimens was monitored using scanning electron microscopy, transmission electron microscopy, high-angle annular dark-field imaging, selected area electron diffraction, and energy dispersive x-ray spectroscopy. Monoclinic cyclosilicate Ca 3 Yb 2 (Si 3 O 9 ) 2 formed from interaction of CYbS apatite with CaO in the CMAS melt at the apatite-CMAS reaction front and continued to nucleate and grow within the residual CMAS in diffusion couples annealed for 1 to 50 h at 1200 °C as well as in those heat treated at 1300 °C for 1 h. Residual CMAS was depleted of Ca when cyclosilicate was present. Dendritic wollastonite (CaSiO3) was observed within the residual CMAS in couples annealed at 1200 and 1300 °C. Ingress of molten CMAS, because of its exponential decrease in viscosity, occurred through open pores and along the grain boundaries of the apatite substrates without any detectable chemical reaction at 1300 and 1400 °C. Results of this study indicate that Ca 2 Yb 8 (SiO 4 ) 6 O 2 apatite has the potential to mitigate the CMAS corrosion up to about 1200 °C but not at higher temperatures.

Narottam P Bansal↗

Spitzer IRS Spectroscopy of the 10 Myr-Old EF Cha Debris Disk: Evidence for Phyllosilicate-Rich Dust in the Terrestrial Zone

We describe Spitzer IRS spectroscopic observations of the approx. 10 Myr-old star, EF Chao Compositional modeling of the spectra from 5 micron to 35 micron confirms that it is surrounded by a luminous debris disk with L(sub D)/L(sub *) approx. 10(exp -3), containing dust with temperatures between 225 K and 430 K characteristic of the terrestrial zone. The EF Cha spectrum shows evidence for many solid-state features, unlike most cold, low-luminosity debris disks but like some other 10-20 Myr-old luminous, warm debris disks (e.g. HD 113766A). The EF Cha debris disk is unusually rich in a species or combination of species whose emissivities resemble that of finely-powdered, laboratory-measured phyllosilicate species (talc, saponite, and smectite), which are likely produced by aqueous alteration of primordial anhydrous rocky materials. The dust and, by inference, the parent bodies of the debris also contain abundant amorphous silicates and metal sulfides, and possibly water ice. The dust's total olivine to pyroxene ratio of approx. 2 also provides evidence of aqueous alteration. The large mass volume of grains with sizes comparable to or below the radiation blow-out limit implies that planetesimals may be colliding at a rate high enough to yield the emitting dust but not so high as to devolatize the planetesimals via impact processing. Because phyllosilicates are produced by the interactions between anhydrous rock and warm, reactive water, EF Cha's disk is a likely signpost for water delivery to the terrestrial zone of a young planetary system.

Currie, Thayne↗

High-Resolution Electron Energy-Loss Spectroscopy (HREELS) Using a Monochromated TEM/STEM

A 200 keV FEI TF20 XT monochromated (scanning) transmission electron microscope funded by NASA's SRLIDAP program is undergoing installation at Lawrence Livermore National Laboratory. Instrument specifications in STEM mode are Cs =1.0 mm, Cc =1.2 mm, image resolution =0.18 nm, and in TEM mode Cs =1.3 mm, Cc =1.3 mm, information limit =0.14 nm. Key features of the instrument are a voltage-stabilized high tension (HT) supply, a monochromator, a high-resolution electron energy-loss spectrometer/energy filter, a high-resolution annular darkfield detector, and a solid-state x-ray energy-dispersive spectrometer. The high-tension tank contains additional sections for 60Hz and high frequency filtering, resulting in an operating voltage of 200 kV plus or minus 0.005V, a greater than 10-fold improvement over earlier systems. The monochromator is a single Wien filter design. The energy filter is a Gatan model 866 Tridiem-ERS high resolution GIF spec d for less than or equal to 0.15 eV energy resolution with 29 pA of current in a 2 nm diameter probe. 0.13 eV has already been achieved during early installation. The x-ray detector (EDAX/Genesis 4000) has a take-off angle of 20 degrees, an active area of 30 square millimeters, and a solid angle of 0.3 steradians. The higher solid angle is possible because the objective pole-piece allows the detector to be positioned as close as 9.47 mm from the specimen. The voltage-stabilized HT supply, monochromator and GIF enable high-resolution electron energy-loss spectroscopy (HREELS) with energy resolution comparable to synchrotron XANES, but with approximately 100X better spatial resolution. The region between 0 and 100 eV is called the low-loss or valence electron energy-loss spectroscopy (VEELS) region where features due to collective plasma oscillations and single electron transitions of valence electrons are observed. Most of the low-loss VEELS features we are detecting are being observed for the first time in IDPs. A major focus of our research is to understand the origin and significance of these features and how they might be exploited to gain insight about IDPs and other meteoritic materials.

Sai, Z. R.↗

Photolysis of Pure Solid O3 and O2 Films at 193nm

We studied quantitatively the photochemistry of solid O3 and O2 films at 193 nm and 22 K with infrared spectroscopy and microgravimetry. Photolysis of pure ozone destroyed O3, but a small amount of ozone remained in the film at high fluence. Photolysis of pure O2 produced O3 in an amount that increased with photon fluence to a stationary level. For both O2 and O3 films, the O3:O2 ratio at large fluences is ?0.07, about two orders of magnitude larger than those obtained in gas phase photolysis. This enhancement is attributed to the increased photodissociation of O2 due to photoabsorption by O2 dimers, a process significant at solid-state densities. We obtain initial quantum yield for ozone synthesis from solid oxygen, phi (O3) = 0.24 0.06, and quantum yields for destruction of O3 and O2 in their parent solids, phi(-O3) = 1.0 0.2 and phi(-O2) = 0.36 0.1. Combined with known photoabsorption cross sections, we estimate probabilities for geminate recombination of 0.5 0.1 for O3 fragments and 0.88 0.03 for oxygen atoms from O2 dissociation. Using a single parameter kinetic model, we deduce the ratio of reaction cross sections for an O atom with O2 vs. O3 to be 0.1 0.2. The general good agreement of the model with the data suggests the validity of the central assumption of efficient energy and spin relaxation of photofragments in the solid prior to their reactions with other species.

Raut, U.↗

All-Solid-State 2.45-to-2.78-THz Source

Sources in the THz range are required in order for NASA to implement heterodyne instruments in this frequency range. The source that has been demonstrated here will be used for an instrument on the SOFIA platform as well as for upcoming astrophysics missions. There are currently no electronic sources in the 2 3- THz frequency range. An electronically tunable compact source in this frequency range is needed for lab spectroscopy as well as for compact space-deployable heterodyne receivers. This solution for obtaining useful power levels in the 2 3- THz range is based on utilizing power-combined multiplier stages. Utilizing power combining, the input power can be distributed between different multiplier chips and then recombined after the frequency multiplication. A continuous wave (CW) coherent source covering 2.48 2.75 THz, with greater than 10 percent instantaneous and tuning bandwidth, and having l 14 W of output power at room temperature, has been demonstrated. This source is based on a 91.8 101.8-GHz synthesizer followed by a power amplifier and three cascaded frequency triplers. It demonstrates that purely electronic solid-state sources can generate a useful amount of power in a region of the electromagnetic spectrum where lasers (solid-state or gas) were previously the only available coherent sources. The bandwidth, agility, and operability of this THz source has enabled wideband, high-resolution spectroscopic measurements of water, methanol, and carbon monoxide with a resolution and signal-to-noise ratio unmatched by other existing systems, providing new insight in the physics of these molecules. Further - more, the power and optical beam quality are high enough to observe the Lamb-dip effect in water. The source frequency has an absolute accuracy better than 1 part in 1012, and the spectrometer achieves sub-Doppler frequency resolution better than 1 part in 108. The harmonic purity is better than 25 dB. This source can serve as a local oscillator for a variety of heterodyne systems, and can be used as a method for precision control of more powerful but much less frequency-agile quantum mechanical terahertz sources.

Mehdi, Imran↗

High Temperature Protonic Conductors

High Temperature Protonic Conductors (HTPC) with the perovskite structure are envisioned for electrochemical membrane applications such as H2 separation, H2 sensors and fuel cells. Successive membrane commercialization is dependent upon addressing issues with H2 permeation rate and environmental stability with CO2 and H2O. HTPC membranes are conventionally fabricated by solid-state sintering. Grain boundaries and the presence of intergranular second phases reduce the proton mobility by orders of magnitude than the bulk crystalline grain. To enhanced protonic mobility, alternative processing routes were evaluated. A laser melt modulation (LMM) process was utilized to fabricate bulk samples, while pulsed laser deposition (PLD) was utilized to fabricate thin film membranes . Sr3Ca(1+x)Nb(2-x)O9 and SrCe(1-x)Y(x)O3 bulk samples were fabricated by LMM. Thin film BaCe(0.85)Y(0.15)O3 membranes were fabricated by PLD on porous substrates. Electron microscopy with chemical mapping was done to characterize the resultant microstructures. High temperature protonic conduction was measured by impedance spectroscopy in wet air or H2 environments. The results demonstrate the advantage of thin film membranes to thick membranes but also reveal the negative impact of defects or nanoscale domains on protonic conductivity.

Dynys, Fred↗

Experimentally Shocked and Altered Basalt: Laboratory Analogs for Calibration of Mars Remote Sensing and In Situ Data

Calciumphosphate (likely chloroapatite) is formed in the alteration experiments and is more abundant in the altered and shocked sample probably due to increased surface area exposed to alteration fluids resulting from shock damage in the form of both brittle and structural deformation to the starting material (Figs 1 & 3). Apatite forms in basic conditions so the closed system alteration experiment must be buffered by the basalt starting material to create a fluid chemistry environment evolving from neutral at the start to alkaline after 21 days at 160 C. Plagioclase feldspar in the unshocked sample (Fig. 2) has undergone a solid-state transformation to maskelynite, a disordered phase that is not manifest in the XRD pattern of the shocked sample (Fig.4). Olivine and ulvospinel that are present in the starting material can be detected by XRD in the shocked and altered sample (Fig. 4). Tungsten from the sample holder used in the shock experiments dominates the XRD pattern of the shocked and altered sample (Fig. 4). Samples were weighed after the alteration experiments to determine mass loss and predict the amount of material available for the planned analyses from the shock experiments. Within the constraints of these experiments, mass loss is negligible. The samples will next be characterized by Moessbauer and Vis-Near IR spectroscopy, the results of which will be compared to the Mars Exploration Rovers and Mars Reconnaissance Orbiter data sets respectively.

Bell, M. S.↗

Experimentally Shocked and Altered Basalt: Laboratory Analogs for Calibration of Mars Remote Sensing and In Situ Data

Calcium phosphate (likely chloroapatite) is formed in the alteration experiments and is more abundant in the altered and shocked sample probably due to increased surface area exposed to alteration fluids resulting from shock damage in the form of both brittle and structural deformation to the starting material (Figs 1 & 3). Apatite forms in basic conditions so the closed system alteration experiment must be buffered by the basalt starting material to create a fluid chemistry environment evolving from neutral at the start to alkaline after 21 days at 160 degrees Centigrade. Plagioclase feldspar in the unshocked sample (Fig. 2) has undergone a solid-state transformation to maskelynite, a disordered phase that is not manifest in the X-ray diffraction pattern of the shocked sample (Fig.4). Olivine and ulvospinel that are present in the starting material can be detected by X-ray diffraction in the shocked and altered sample (Fig. 4). Tungsten from the sample holder used in the shock experiments dominates the X-ray diffraction pattern of the shocked and altered sample (Fig. 4). Samples were weighed after the alteration experiments to determine mass loss and predict the amount of material available for the planned analyses from the shock experiments. Within the constraints of these experiments, mass loss is negligible. The samples will next be characterized by Moessbauer and Vis-Near Infrared spectroscopy, the results of which will be compared to the Mars Exploration Rovers and Mars Reconnaissance Orbiter data sets respectively.

Bell, M. S.↗

Nova V2362 Cygni (Nova Cygni 2006): Spitzer, Swift, and Ground-Based Spectral Evolution

Nova V2362 Cygni has undergone a number of very unusual changes. Ground-based spectroscopy initially revealed a normal sequence of events: the object faded and its near-infrared emission lines gradually shifted to higher excitation conditions until about day 100 when the optical fading reversed and the object slowly brightened. This was accompanied by a rise in the Swift X-ray telescope flux and a sudden shift in excitation of the visible and IR spectrum back to low levels. The new lower excitation spectrum revealed broad line widths and many P-Cygni profiles, all indicative of the ejection of a second shell. Eventually, dust formed, the X-ray brightness -- apparently unaffected by dust formation -- peaked and then declined, and the object faded at all wavelengths. The Spitzer dust spectra revealed a number of solid-state emission features that, at this time, are not identified.

Lynch, David K.↗

NASA Tech Briefs, June 2003

Topics covered include: Nulling Infrared Radiometer for Measuring Temperature; The Ames Power Monitoring System; Hot Films on Ceramic Substrates for Measuring Skin Friction; Probe Without Moving Parts Measures Flow Angle; Detecting Conductive Liquid Leaking from Nonconductive Pipe; Adaptive Suppression of Noise in Voice Communications; High-Performance Solid-State W-Band Power Amplifiers; Microbatteries for Combinatorial Studies of Conventional Lithium-Ion Batteries; Correcting for Beam Aberrations in a Beam-Waveguide Antenna; Advanced Rainbow Solar Photovoltaic Arrays; Metal Side Reflectors for Trapping Light in QWIPs; Software for Collaborative Engineering of Launch Rockets; Software Assists in Extensive Environmental Auditing; Software Supports Distributed Operations via the Internet; Software Estimates Costs of Testing Rocket Engines; yourSky: Custom Sky-Image Mosaics via the Internet; Software for Managing Inventory of Flight Hardware; Lower-Conductivity Thermal-Barrier Coatings; Process for Smoothing an Si Substrate after Etching of SiO2; Flexible Composite-Material Pressure Vessel; Treatment to Destroy Chlorohydrocarbon Liquids in the Ground; Noncircular Cross Sections Could Enhance Mixing in Sprays; Small, Untethered, Mobile Roots for Inspecting Gas Pipes; Paint-Overspray Catcher; Preparation of Regular Specimens for Atom Probes; Inverse Tomo-Lithography for Making Microscopic 3D Parts; Predicting and Preventing Incipient Flameout in Combustors; MEMS-Based Piezoelectric/Electrostatic Inchworm Actuator; Metallized Capillaries as Probes for Raman Spectroscopy; Adaptation of Mesoscale Weather Models to Local Forecasting; Aerodynamic Design using Neural Networks; Combining Multiple Gyroscope Outputs for Increased Accuracy; and Improved Collision-Detection Method for Robotic Manipulator.

Source record↗

AstroBiology Explorer Mission Concepts (ABE/ASPIRE)

The AstroBiology Explorer (ABE) and the Astrobiology Space InfraRed Explorer (ASPIRE) Mission Concepts are two missions designed to address the questions (1) Where do we come from? and (2) Are we alone? as outlined in NASA s Origins Program using infrared spectroscopy to explore the identity, abundance, and distribution of molecules of astrobiological importance throughout the Universe. The ABE mission s observational program is focused on six tasks to: (1) Investigate the evolution of ice and organics in dense clouds and star formation regions, and the young stellar/planetary systems that form in them; (2) Measure the evolution of complex organic molecules in stellar outflows; (3) Study the organic composition of a wide variety of solar system objects including asteroids, comets, and the planets and their satellites; (4) Identify organic compounds in the diffuse interstellar medium and determine their distribution , abundance, and change with environment; (5) Detect and identify organic compounds in other galaxies and determine their dependence on galactic type; and (6) Measure deuterium enrichments in interstellar organics and use them as tracers of chemical processes. The ASPIRE mission s observational program expands upon ABE's core mission and adds tasks that (7) Address the role of silicates in interstellar organic chemistry; and (8) Use different resolution spectra to assess the relative roles and abundances of gas- and solid-state materials. ABE (ASPIRE) achieves these goals using a highly sensitive, cryogenically-cooled telescope in an Earth drift-away heliocentric orbit, armed with a suite of infrared spectrometers that cover the 2.5-20(40) micron spectral region at moderate spectral resolution (R>2000). ASPIRE's spectrometer complement also includes a high-resolution (R>25,000) module over the 4-8 micron spectral region. Both missions target lists are chosen to observe a statistically significant sample of a large number of objects of varied types in support of the tasks outline above. The ABE and ASPIRE mission lifetimes are designed to be 14 months and 3 years, respectively, both with significant cryogen and propellant lifetime margins to support an extended observing campaign. The ABE/ASPIRE mission concepts and their supporting Science Teams are led by Principal Investigator Dr. Scott Sandford of NASA s Ames Research Center, with industry partner Ball Aerospace Technologies Ltd., and managed by Jet Propulsion Laboratory. The ABE/ASPIRE Science Operations will be carried out at NASA s Ames Research Center, and the ABE/ASPIRE database will be archived at Caltech/IPAC.

Sandford, Scott↗

Diode Laser Velocity Measurements by Modulated Filtered Rayleigh Scattering

The ability of solid-state lasers to be tuned in operating frequency at MHz rates by input current modulation, while maintaining a relatively narrow line-width, has made them useful for spectroscopic measurements. Their other advantages include low cost, reliability, durability, compact size, and modest power requirements, making them a good choice for a laser source in micro-gravity experiments in drop-towers and in flight. For their size, they are also very bright. In a filtered Rayleigh scattering (FRS) experiment, a diode laser can be used to scan across an atomic or molecular absorption line, generating large changes in transmission at the resonances for very small changes in frequency. The hyperfine structure components of atomic lines of alkali metal vapors are closely spaced and very strong, which makes such atomic filters excellent candidates for sensitive Doppler shift detection and therefore for high-resolution velocimetry. In the work we describe here we use a Rubidium vapor filter, and work with the strong D(sub 2) transitions at 780 nm that are conveniently accessed by near infrared diode lasers. The low power output of infrared laser diodes is their primary drawback relative to other laser systems commonly used for velocimetry. However, the capability to modulate the laser frequency rapidly and continuously helps mitigate this. Using modulation spectroscopy and a heterodyne detection scheme with a lock-in amplifier, one can extract sub-microvolt signals occurring at a specific frequency from a background that is orders of magnitude stronger. The diode laser modulation is simply achieved by adding a small current modulation to the laser bias current. It may also be swept repetitively in wavelength using an additional lower frequency current ramp.

Mach, J. J.↗

Quad-Chip Double-Balanced Frequency Tripler

Solid-state frequency multipliers are used to produce tunable broadband sources at millimeter and submillimeter wavelengths. The maximum power produced by a single chip is limited by the electrical breakdown of the semiconductor and by the thermal management properties of the chip. The solution is to split the drive power to a frequency tripler using waveguides to divide the power among four chips, then recombine the output power from the four chips back into a single waveguide. To achieve this, a waveguide branchline quadrature hybrid coupler splits a 100-GHz input signal into two paths with a 90 relative phase shift. These two paths are split again by a pair of waveguide Y-junctions. The signals from the four outputs of the Y-junctions are tripled in frequency using balanced Schottky diode frequency triplers before being recombined with another pair of Y-junctions. A final waveguide branchline quadrature hybrid coupler completes the combination. Using four chips instead of one enables using four-times higher power input, and produces a nearly four-fold power output as compared to using a single chip. The phase shifts introduced by the quadrature hybrid couplers provide isolation for the input and output waveguides, effectively eliminating standing waves between it and surrounding components. This is accomplished without introducing the high losses and expense of ferrite isolators. A practical use of this technology is to drive local oscillators as was demonstrated around 300 GHz for a heterodyne spectrometer operating in the 2-3-THz band. Heterodyne spectroscopy in this frequency band is especially valuable for astrophysics due to the presence of a very large number of molecular spectral lines. Besides high-resolution radar and spectrographic screening applications, this technology could also be useful for laboratory spectroscopy.

Lin, Robert H.↗

In-Flight Performance of the Soft X-Ray Spectrometer Detector System on ASTRO-H

The SXS instrument was launched aboard the Astro-H observatory on February 17, 2016. The SXS spectrometer is based on a high sensitivity x-ray calorimeter detector system that has been successfully deployed in many ground and sub-orbital spectrometers. The instrument was to provide essential diagnostics for nearly every class of x-ray emitting objects from the atmosphere of Jupiter to the outskirts of galaxy clusters, without degradation for spatially extended objects. The SXS detector system consisted of a 36-pixel cryogenic microcalorimeter array operated at a heat sink temperature of 50 mK. In pre-flight testing, the detector system demonstrated a resolving power of better than 1300 at 6 keV with a simultaneous band-pass from below 0.3 keV to above 12 keV with a timing precision better than 100 microsecond. In addition, a solid-state anti-coincidence detector was placed directly behind the detector array for background suppression. The detector error budget included the measured interference from the SXS cooling system and the spacecraft. Additional margin for on-orbit gain-stability, and on-orbit spacecraft interference were also included predicting an on-orbit performance that meets or exceeds the 7 eV FWHM at 6 keV requirement. The actual on-orbit spectral resolution was better than 5 eV FWHM at 6 keV, easily satisfying the instrument requirement. Here we discuss the actual on-orbit performance of the SXS detector system and compare this to performance in pre-flight testing and the on-orbit predictions. We will also discuss the on-orbit gain stability, additional on-orbit interference, and measurements of the on-orbit background.

X-ray astrophysics↗

Synthesis, Structure, Characterization, and Decomposition of Nickel Dithiocarbamates: Effect of Precursor Structure and Processing Conditions on Solid-State Products

Single-crystal X-ray structures of four nickel dithiocarbamate complexes, the homoleptic mixed-organic bis-dithiocarbamates Ni[S2CN(isopropyl)(benzyl)]2, Ni[S2CN(ethyl)(n-butyl)]2, and Ni[S2CN(phenyl)(benzyl)]2, as well as the heteroleptic mixed-ligand complex NiCl[P(phenyl)3][(S2CN(phenyl)(benzyl)], were determined. Synthetic, spectroscopic, structural, thermal, and sulfide materials studies are discussed in light of prior literature. The spectroscopic results are routine. A slightly distorted square-planar nickel coordination environment was observed for all four complexes. The organic residues adopt conformations to minimize steric interactions. Steric effects also may determine puckering, if any, about the nickel and nitrogen atoms, both of which are planar or nearly so. A trans-influence affects the Ni-S bond distances. Nitrogen atoms interact with the CS2 carbons with a bond order of about 1.5, and the other substituents on nitrogen display transoid conformations. There are no strong intermolecular interactions, consistent with prior observations of the volatility of nickel dithiocarbamate complexes. Thermogravimetric analysis of the homoleptic species under inert atmosphere is consistent with production of 1:1 nickel sulfide phases. Thermolysis of nickel dithiocarbamates under flowing nitrogen produced hexagonal or -NiS as the major phase; thermolysis under flowing forming gas produced millerite (-NiS) at 300 C, godlevskite (Ni9S8) at 325 and 350 C, and heazlewoodite (Ni3S2) at 400 and 450 C. Failure to exclude oxygen results in production of nickel oxide. Nickel sulfide phases produced seem to be primarily influenced by processing conditions, in agreement with prior literature. Nickel dithiocarbamate complexes demonstrate significant promise to serve as single-source precursors to nickel sulfides, a quite interesting family of materials with numerous potential applications.

microscopy↗