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534 records · Page 30

Highly Reversible Plating/Stripping of Porous Zinc Anodes for Multivalent Zinc Batteries

Zinc continues to garner immense interest due to its versatility as an anode material in several configurations utilizing either alkaline or mild-pH electrolytes. Current research on using mild-pH electrolytes has improved the rechargeability aspect of Zn-based batteries since Zn2+ is solely utilized for plating/stripping of Zn. Several studies have incorporated Zn metal foils, yet, dramatic improvements can be achieved by expressing Zn as a porous structure. Herein, we use a quasi-pulsed electrodeposition process to prepare a conformal Zn coating onto 3D porous copper foam. By tuning the electrodeposition parameters, we achieved an optimal Zn coating that undergoes reversible plating/stripping when tested in symmetric Zn cells, which supported a low overpotential of ~60 mV for up to 100 cycles. We further investigated changes in the surface morphology by studying the Zn surface of both foil and 3D structure using scanning electron microscopy and X-ray micro-computed tomography. Both techniques showed that the Zn foil undergoes dramatic alterations at the surface, which results in inhomogeneous deposition of Zn, whereas the 3D form exhibited minimal changes. Lastly, we paired both Zn foil and 3D Zn with vanadium oxide and demonstrated that the porous structure supports high rate capability and high specific capacity.

25 ENERGY STORAGE↗

Effect of Impurities on the Redox Properties of Goethite

Iron oxide minerals regulate the flux of electrons in the environment and are important hosts for trace and minor, yet critical, elements. Here, we present the first evidence of a direct link between the local coordination environments of Ni and Zn and the redox properties of their host phase goethite (α-FeOOH), the most abundant Fe(III) (oxyhydr)oxide at Earth’s surface. Here, we used aqueous redox measurements to show that the redox potential E H 0 , and hence the mineral’s stability, follows the order: pure goethite ≥ Zn-goethite > Ni-goethite. Parallel X-ray absorption and scattering measurements demonstrate, using quantum-informed analysis, that the local coordination environment of the smaller impurity, Ni, causes more bulk strain energy than Zn, which nearly accounts for the difference in E H 0 between Ni- and Zn-goethite. Our theory-informed, experimental study reveals how two common impurities affect the stability of goethite with implications for the biogeochemical reactivity of Fe(III) (oxyhydr)oxide in mediating elemental and electron fluxes in the environment.

42 ENGINEERING↗

Moisture interaction and stability of ZOT (Zinc Orthotitanate) thermal control spacecraft coating

Two of the many performance requirements of the zinc orthotitanate (ZOT) ceramic thermal control paint covering parts of the Jupiter-bound Galileo spacecraft are that it be sufficiently electrically conductive so as to prevent electrostatic discharge (ESD) damage to onboard electronics and that it adhere to and protect the substrate from corrosion in terrestrial environments. The bulk electrical resistivity of ZOT on an aluminum substrate was measured over the ranges 22 C to 90 C and 0 percent RH to 100 percent RH, and also in soft (10 (minus 2) Torr) and hard (10 (minus 7) Torr) vacuums. No significant temperature dependence was evident, but measured resistivity values ranged over 9 orders of magnitude: 10 to the 5th power ohm-cm at 100 percent RH greater than 10 to the 12th power ohm-cm in a hard vacuum. The latter value violates the ESD criterion for a typical 0.019 cm thick coating. The corrosion study involved exposing typical ZOT substrate combinations to two moisture environments - 30 C/85 percent RH and 85 C/85 percent RH - for 2000 hours, during which time the samples were periodically removed for front-to-back electrical resistance and scratch/peel test measurements. It was determined that the ZOT/Al and ZOT/Mg systems are stable (no ZOT delamination), although some corrosion (oxide formation) and resistivity increases observed among the ZOT/Mg samples warrant that exposure of some parts to humid environments be minimized.

Mon, Gordon R.↗

On the New Oxyarsenides Eu 5 Zn 2 As 5 O and Eu 5 Cd 2 As 5 O

The new quaternary phases Eu5Zn2As5O and Eu5Cd2As5O have been synthesized by metal flux reactions and their structures have been established through single-crystal X-ray diffraction. Both compounds crystallize in the centrosymmetric space group Cmcm (No. 63, Z = 4; Pearson symbol oC52), with unit cell parameters a = 4.3457(11) Å, b = 20.897(5) Å, c = 13.571(3) Å; and a = 4.4597(9) Å, b = 21.112(4) Å, c = 13.848(3) Å, for Eu5Zn2As5O and Eu5Cd2As5O, respectively. The crystal structures include one-dimensional double-strands of corner-shared MAs4 tetrahedra (M = Zn, Cd) and As–As bonds that connect the tetrahedra to form pentagonal channels. Four of the five Eu atoms fill the space between the pentagonal channels and one Eu atom is contained within the channels. An isolated oxide anion O2– is located in a tetrahedral hole formed by four Eu cations. Applying the valence rules and the Zintl concept to rationalize the chemical bonding in Eu5M2As5O (M = Zn, Cd) reveals that the valence electrons can be counted as follows: 5 × [Eu2+] + 2 × [M2+] + 3 × [As3–] + 2 × [As2–] + O2–, which suggests an electron-deficient configuration. The presumed h+ hole is confirmed by electronic band structure calculations, where a fully optimized bonding will be attained if an additional valence electron is added to move the Fermi level up to a narrow band gap (Eu5Zn2As5O) or pseudo-gap (Eu5Cd2As5O). In order to achieve such a formal charge balance, and hence, narrow-gap semiconducting behavior in Eu5M2As5O (M = Zn, Cd), europium is theorized to be in a mixed-valent Eu2+/ Eu3+ state.

36 MATERIALS SCIENCE↗

New Anti-Corrosive Coatings with Resin-Bonded Polyaniline and Related Electroactive Groups

It is already known that polyaniline (an electroactive polymer) functions as a corrosion inhibitor for steel and in view of the fact that it is known to perform in the presence of hydrochloric acid, it has been considered likely that it may be useful to NASA for protecting launch structures at KSC which are exposed to not only continual ocean-side salt spray but also to hydrochloric acid at the times that solid-fuel boosters are fired. The currently used zinc-rich silicate-bonded coating is not wholly protective against the hydrochloric acid. Water pollution from zinc salts is another concern. Other earlier and concurrent NASA sponsored projects have been focussed on polyaniline specifically. Our project, administered for NASA by Dr. K. Thompson of KSC and these more-specifically polyaniline-related projects are included in a CRADA coordinated by Dr. F. Via of Akzo Nobel. A parallel project at Polytechnic under Prof K. Levon concentrated more specifically on polyaniline with various dopants. Our exploratory project reported herein was aimed at broadening the range of such corrosion inhibitors, to give protective paint compounders a wider latitude for adding corrosion inhibitors having polyaniline-like performance, and thus we diverged in several probing directions from polyaniline. Our working hypothesis was that physical variants of polyaniline, such as supported formulations on pigments or carriers, and chemical variants of polyaniline, including those having no electroconductive character, may have enhanced anticorrosion activity. We also hypothesized that small (non-polymeric) molecules having structures related to those occurring in polyaniline, may be active as corrosion inhibitors. We did preliminary testing, using an ASTM salt spray method at a nearby commercial paint testing laboratory. Our most interesting findings were that a non-electroconductive meta-isomer of polyaniline showed some corrosion activity, suggesting that the features of the polyaniline molecule associated with conductivity are not necessary for the anticorrosion action. Also, signtficantly, small molecular weight aromatic diamines and diimines resembling the reduced and the oxidized repeating unit in polyaniline showed an interesting degree of anticorrosive activity, suggesting that the polymeric feature of polyaniline is not necessary for anticorrosion action.

Weil, Edward D.↗

Generalizable, tunable control of divalent cation solvation structure via mixed anion contact ion pair formation

Multivalent batteries are a promising new technology for energy storage, but they face challenges to developing suitable electrolytes that can support reversible deposition/dissolution at the metal anode and enable compatibility with high voltage oxide cathode materials. Here, in this work, we investigate the solvation behavior of Zn 2+ , Mg 2+ , Ca 2+ and Cu 2+ in mixed anion electrolytes containing TFSI - and Cl - . Raman and nuclear magnetic resonance spectroscopies are utilized to probe the bulk solvation structure of these electrolytes and demonstrate that mixed anion contact ion pairs (CIPs) are formed in all four systems, indicating this behavior is likely general to divalent cations. Furthermore, the relative population of mixed anion CIPs can be tuned by controlling the relative ratio of TFSI : Cl, with significant CIP populations observed even at low relative fractions of Cl - . These findings imply that modifying the anion chemistry can easily adjust the solvation structure of bulk cations, which has important implications for the development of next-generation electrolytes. By understanding the factors that influence the formation of mixed anion CIPs, we can design systems that promote the formation of electrochemically-active solvation structures that can enable multivalent batteries with improved performance and lifetimes.

25 ENERGY STORAGE↗

Sulfur Species in Zinc-Rich Condylar Zones of a Rat Temporomandibular Joint

We performed synchrotron-based micro-X-ray absorption near-edge spectroscopy (µ-XANES) coupled with micro-X-ray fluorescence (µ-XRF) for the identification of elements that included biometal zinc (Zn) and nonmetal sulfur (S) (and its species) in the condylar zones of a rat temporomandibular joint (TMJ). Zone-specific spatial localization of biometal Zn and nonmetal S from a materials viewpoint when correlated with hypoxia inducible factor-1α (HIF-1α) (a surrogate for tissue oxygenation) can provide insights into Zn-specific redox pathways at the vulnerable subchondral interface. Histologic localization of Zn, HIF-1α, and sulfur-rich proteoglycans (PGs) were mapped using an optical microscope. The µ-XRF maps coupled with site-specific micro-X-ray diffraction (µ-XRD) patterns were used to underline Zn-incorporated biological apatite in the subchondral bone and the bone of a rat TMJ condyle. Results demonstrated an association between Zn, PG, and HIF-1α histologic maps with µ-XRF, µ-XANES, and µ-XRD data and provided insights into plausible biological S species in Zn-enriched zones of a rat TMJ condyle. Spatially localized Zn and S underscore their roles in cell and tissue functions in a zone-specific manner. Elemental Zn with organic and inorganic S species at the cartilage-bone interface and the biomineral phase of Zn-enriched biological apatite from subchondral bone to condylar bone were ascertained using µ-XRF-XANES and µ-XRF-XRD. The coupled µ-XRF-XANES in situ complemented with µ-XRF-XRD in situ and immunohistochemistry provided valuable biological insights into zone-specific biological pathways in rat TMJ condyles. Based on these data, we present a workflow to reliably map and correlate S species within Zn-enriched regions of cartilage, bone, and their interface. We suggest the use of this correlative and complementary microspectroscopic spatial information for zone-specific localization of biometal Zn and nonmetal S to gain insights into plausible microanatomy-specific oxidative stress in the TMJ.

apatites↗

Zinc Speciation and Propane Dehydrogenation in Zn/H-ZSM-5 Catalysts

Zn/H-ZSM-5 catalysts have been frequently investigated for propane dehydrogenation (PDH); however, the active site remains unresolved due to the complexity of the system. We employed in situ FTIR spectroscopy and a kinetics method to correlate the Zn speciation and PDH activity in Zn/H-ZSM-5 with two Si/Al ratios (15 and 39) and a range of Zn/Al ratios (0–1.7). Incremental additions of zinc show that Zn 2+ sites are preferentially formed on H-ZSM-5 over a fraction of paired Al sites followed by [Zn-O-Zn] 2+ and [ZnOH] + sites and then ZnO x clusters. The [Zn-OH] + and [Zn-O-Zn] 2+ sites in H-ZSM-5 are more active and selective than isolated Zn 2+ for PDH. [Zn-OH] + species sublimate over time on stream, leading to catalyst deactivation, while [Zn-O-Zn] 2+ species are stable even after high-temperature reduction (750 °C for 60 min). Three distinct Zn sites ([Zn-O-Zn] 2+ , Zn 2+ , and [ZnOH] + ) show a similar propane reaction order (close to 1) and H 2 reaction order (close to 0). Combined with the lack of Zn hydride when propane flows over the catalyst at 550 °C, it is concluded that propane adsorption and dissociation is a rate-determining step and H 2 desorption is fast. This work indicates that the preparation of H-ZSM-5 with abundant Al pairs may be a strategy to form stable and selective Zn/H-ZSM-5 catalysts for propane dehydrogenation. Furthermore, it is also highlighted that examining the effect of both metal/Al ratios and Al distribution of the zeolite is crucial in identifying the metal cations in metal–zeolite systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rechargeable Alkaline Zinc/Copper Oxide Batteries

Resurrecting a battery chemistry thought to be only primary, we demonstrate the first example of a rechargeable alkaline zinc/copper oxide battery. With the incorporation of a Bi 2 O 3 additive to stabilize the copper oxide-based conversion cathode, Zn/(CuO–Bi 2 O 3 ) cells are capable of cycling over 100 times at >124 W h/L, with capacities from 674 mA h/g (cycle 1) to 362 mA h/g (cycle 150). The crucial role of Bi 2 O 3 in facilitating the electrochemical reversibility of Cu 2 O, Cu(OH) 2 , and Cu o was supported by scanning and transmission electrochemical microscopy, cyclic voltammetry, and rotating ring-disc electrode voltammetry and monitored via operando energy-dispersive X-ray diffraction measurements. Bismuth was identified as serving two roles, decreasing the cell resistance and promoting Cu(I) and Cu(II) reduction. Additionally, to mitigate the capacity losses of long-term cycling CuO cells, we demonstrate two limited depth of discharge (DOD) strategies. First, a 30% DOD (202 mA h/g) retains 99.9% capacity over 250 cycles. Second, the modification of the CuO cathode by the inclusion of additional Cu metal enables performance at very high areal capacities of ~40 mA h/cm 2 and unprecedented energy densities of ~260 W h/L, with near 100% Coulombic efficiency. This work revitalizes a historically primary battery chemistry and opens opportunity to future works in developing copper-based conversion cathode chemistries for the realization of low-cost, safe, and energy-dense secondary batteries.

25 ENERGY STORAGE↗

Zn acceptors in β-Ga 2 O 3 crystals

Electron paramagnetic resonance (EPR) is used to identify and characterize neutral zinc acceptors in Zn-doped β-Ga 2 O 3 crystals. Two EPR spectra are observed at low temperatures, one from Zn ions at tetrahedral Ga(1) sites (the $Zn$$^{0}_{Ga 1}$ acceptor) and one from Zn ions at octahedral Ga(2) sites (the $Zn$$^{0}_{Ga 2}$ acceptor). These Zn acceptors are small polarons, with the unpaired spin localized in each case on a threefold coordinated oxygen O(I) ion adjacent to the Zn ion. Resolved hyperfine interactions with neighboring 69 Ga and 71 Ga nuclei allow the EPR spectra from the two acceptors to be easily distinguished: $Zn$$^{0}_{Ga 1}$ acceptors interact equally with two Ga(2) ions and $Zn$$^{0}_{Ga 2}$ acceptors interact unequally with a Ga(1) ion and a Ga(2) ion. The as-grown crystals are compensated, with the Zn ions initially present as singly ionized acceptors ($Zn$$^{-}_{Ga 1}$ and $Zn$$^{-}_{Ga 2}$). Exposing a crystal to 325 nm laser light, while being held at 140 K, primarily produces neutral $Zn$$^{0}_{Ga 2}$ acceptors when photoinduced holes are trapped at $Zn$$^{-}_{Ga 2}$ acceptors. This suggests that there may be significantly more Zn ions at Ga(2) sites than at Ga(1) sites. Warming the crystal briefly to room temperature, after removing the light, destroys the EPR spectrum from the shallower $Zn$$^{0}_{Ga 2}$ acceptors and produces the EPR spectrum from the more stable $Zn$$^{0}_{Ga 1}$ acceptors. Furthermore, the $Zn$$^{0}_{Ga 2}$ acceptors decay in the 240–260 K region with a thermal activation energy near 0.65 eV, similar to $Mg$$^{0}_{Ga 2}$ acceptors, whereas the slightly deeper $Zn$$^{0}_{Ga 1}$ acceptors decay close to room temperature with an approximate thermal activation energy of 0.78 eV.

36 MATERIALS SCIENCE↗

Shockwave/Boundary-Layer Interaction Studies Performed in the NASA Langley 20-Inch Mach 6 Air Tunnel

This paper highlights results from a collaborative study performed by The University of Tennessee Space Institute (UTSI) and NASA Langley Research Center on the Shockwave/Boundary-Layer Interaction (SWBLI) generated by a cylindrical protuberance on a flat plate in a Mach 6 flow. The study was performed in the 20-Inch Mach 6 Air Tunnel at NASA Langley Research Center and consisted of two separate entries. In the first entry, simultaneous high-speed schlieren and high-speed pressure-sensitive paint (PSP) imaging – which was performed for the first time in the 20-Inch Mach 6 facility at NASA Langley – were performed as well as simultaneous high-speed schlieren and oil-flow imaging. In the second entry, the model configuration was modified to increase the size of the interaction region. High-speed schlieren and infrared thermography (IR) surface imaging were performed in this second entry. The goal of these tests was to characterize the SBLI in the presence of a laminar, transitional, and turbulent boundary layer using high-speed optical imaging techniques. AoA = sting angle-of-attack (°) dcylinder = cylinder diameter (mm) dtrip = cylindrical tripping element diameter (mm) Δshock = shock stand-off distance (mm) hcylinder = cylinder height (mm) htrip = cylindrical tripping element height (mm) HSS = high-speed schlieren M∞ = freestream Mach number PSP = pressure-sensitive paint Re∞ = freestream unit Reynolds number (m-1) SWBLI = shockwave/boundary-layer interaction θplate = model plate angle (°) Introduction his paper highlights two experimental entries performed in the 20-Inch Mach 6 Air Blowdown Tunnel at NASA Langley Research Center in collaboration with The University of Tennessee Space Institute (UTSI). The purpose of these entries was to characterize the dynamic shockwave/boundary-layer interaction (SWBLI) between a vertical cylinder on a flat plate and laminar, transitional (XSWBLI), and turbulent (SWTBLI) boundary layers with a freestream Mach number of 6 using non-intrusive optical diagnostics. Experiments performed by Murphree et al.1,2 were among the first to specifically characterize XSWBLI induced by a vertical cylinder on a flat plate geometry using several optical measurement techniques. Recent optical studies of XSWBLI phenomenon have been performed by UTSI at Mach 2 in their low-enthalpy blow wind tunnel3-8 and by Texas A&M University and UTSI at Mach numbers of 6 and 7 in their Adjustable Contour Expansion wind tunnel.9 The experiments described in this paper were intended to complement previous studies by expanding the freestream unit Reynolds number range, Re∞, over which the XSWBLI phenomena has been observed. Additionally these experiments, made possible under NASA’s new facility funding model under the Aeronautics Evaluation and Test Capabilities (AETC) project, promoted collaboration between university and NASA researchers. The initial entry in the 20-Inch Mach 6 Air Tunnel at NASA Langley occurred in December of 2016. Originally, testing was to occur in November of 2016 in the 31-Inch Mach 10 Air Tunnel at NASA Langley. This facility was chosen so that the XSWBLI phenomenon could be observed at much higher Mach numbers than had previously been attempted in ground test experiments. The model selected for this experiment, a 10° half-angle wedge with a sharp leading edge (described in detail in section II.B), had previously been used by Danehy et al. [10] for boundary layer transition studies using the nitric oxide planar laser-induced fluorescence (NO PLIF) flow visualization technique. In that work, it was determined that transition could be induced downstream of a single htrip = 1-mm tall, dtrip = 4-mm diameter cylindrical tripping element and that the streamwise location of the transition could be changed for a single Re∞ by changing the model angle-of-attack (AoA) (see Fig. A3 in Ref. [10] for more details). Based on the findings of that work, a decision was made to use the wedge model with the cylindrical tripping element to trip the boundary layer flow ahead of a cylindrical protuberance in order to achieve a XSWBLI. Unfortunately, the 31-Inch Mach 10 facility had been taken offline for repairs in October of 2016 and a decision was made to move the test to the 20-Inch Mach 6 facility. Since the behavior of the boundary layer with the chosen model configuration had not been studied before in that facility and the available test time was limited, the entry was considered to be exploratory and was used to collect spatially-resolved and time-resolved flow and surface visualization data that would be used to inform a second entry. Test techniques included simultaneous high-speed schlieren (HSS) captured at 160 kHz and high-speed pressure sensitive paint captured at 10 kHz as well as oil flow visualization, captured at 750 Hz. The second entry in the 20-Inch Mach 6 facility occurred in June and July of 2017. In this follow-on test, modifications to the wind tunnel model were made based on observations made during the first entry and included removing the cylindrical tripping element, increasing the size of the cylinder used to induce the SWBLI to increase the size of the interaction while simultaneously improving spatial resolution, and using a swept ramp array, similar to that described in Ref. [11], to trip the flow to turbulence. Simultaneous HSS (captured at 140 kHz, 100 kHz, and 40 kHz) and conventional IR thermography (captured at 30 Hz) imaging were performed simultaneously in this follow-on entry. This paper is intended to serve as a summary of the work performed during these two entries, to detail lessons learned from each entry, and to highlight some of the datasets acquired. Details on the experimental setup, model configuration, and techniques used are provided. Papers providing a more rigorous analysis of data acquired during the second entry, including statistical, spectral, and modal decomposition methods, can be found in Refs. [12,13]. An entry examining XSWBLI in the 31-Inch Mach 10 Blowdown Wind Tunnel facility is currently planned for mid-to-late calendar year 2019, pending the success of facility repairs. The work performed and described in this paper and the upcoming entry in the 31-Inch Mach 10 facility at NASA Langley have been made possible by NASA’s new facility funding model under the Aeronautics Evaluation and Test Capabilities (AETC) project. Wind Tunnel Facility All experiments discussed in this paper were performed in the 20-Inch Mach 6 Air Tunnel at NASA Langley Research Center. Specific details pertaining to this facility can be found in Refs. [14,15], with only a brief description of the facility provided here. For both entries, the nominal freestream unit Reynolds number was varied between 1.8×106 m-1 (0.5×106 ft-1) and 26.3×106 m-1 (8×106 ft-1). The nominal stagnation pressure was varied between 0.21 MPa and 3.33 MPa and the nominal stagnation temperature was varied between 480 K and 520 K to achieve the desired Re∞ condition. For all runs, the nominal freestream Mach number was 6. The nearly square test section is 520.7-mm (20.5-inches) wide by 508-mm (20-inches) high. Two 431.8-mm (17-inch) diameter windows made of Corning 7940, Grade 5F schlieren-quality glass serve as the side walls of the tunnel and provide optical access for the high-speed schlieren measurements. A rectangular window made of the same material as the side windows served as the top wall of the test section and provided optical access for the high-speed PSP and oil flow measurements. For the second entry, this top window was replaced with a Zinc Selenide (ZnSe) window with an anti-reflection coating capable of passing IR wavelengths between 8μm and 12μm with greater than 98% transmittance. The model was sting supported by a strut attached to a hydraulic system that allows for the model pitch angle to be adjusted between -5° to +55°. For the first entry, an initial pitch/pause sweep of the model AoA was performed to observe the resulting SWBLI. Ultimately, however, the sting pitch angle for this entry was fixed at +10.0° so that the angle of the top surface of the wedge relative to the streamwise axis of the tunnel (referred to herein as the plate angle, θplate), was θplate = 0°. For the second entry, θplate = 0° and θplate = -13.25° were initially tested with the swept ramp array (discussed in the following section) to determine which orientation produced conditions most favorable for XSWBLI to occur based on the heating signatures observed over the top surface of the model in the IR thermography images. Based on these initial tests, θplate = -13.25° was set for the remainder of the runs in the second entry. For both entries, any model changes were performed in a housing located beneath the closed test section. Prior to performing a run of the tunnel, the housing was sealed and the tunnel started. Once the appropriate freestream conditions were achieved, the model was injected into the test section using a hydraulic injection system. B. Model Geometry For all runs, a 10° half-angle (20° full-angle) wedge model with a sharp leading edge was used. The model is described in detail in Refs. [10,16]. The top surface of the sharp leading edge of the model extended 47.8 mm from its upstream-most edge to a junction with the upstream edge of a stainless steel top plate that then extended an (a) (c) (b) Fig. 1 (a) Schematic of top surface of wedge model with gas seeding insert, (b) perspective view of the model in the 20-Inch Mach 6 tunnel with centerline pressure orifices on sharp leading edge, and (c) a perspective view of the model with stainless steel (top) and SLA middle insert (bottom) during the first entry. Flow occurs from left to right.

Bathel, Brett F.↗