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At least 487 records · Page 27

Experimental Studies of Graphene-Coated Polymer Electrolyte Membranes for Direct Methanol Fuel Cells

The two main technical limitations of direct methanol fuel cells (DMFCs) are the slow kinetic reactions of the methanol oxidation reaction (MOR) in the anode and the crossing over of unreacted methanol through the proton exchange membrane (PEM). It is a common practice to use Nafion membranes as PEMs, which have high ion exchange capacity. However, Nafion-based membranes also have high fuel permeability, decreasing fuel utilization, and reducing the potential power density. This article focuses on using graphene-coated (Gr-coated) PEMs to reduce fuel crossover. Protons can permeate across graphene, and thus, it can be employed in various devices as a proton conductive membrane. Here, we report the efficiency of Gr-coated Nafions. We tested performance and crossover at three different temperatures with four different fuel concentrations and compared it to a Nafion PEM that underwent the same test conditions. We found that the adhesion of Gr on to PEMs is insufficient for prolonging fuel cell operation, resulting in Gr delamination at high temperatures and higher fuel crossover values compared to lower temperature testing. Furthermore, the results for 7.5M methanol fuel show a reduction of up to 25% in methanol crossover, translating to a peak power density that increases from 3.9 to 9.5 mW/cm 2 when using a Gr-coated PEM compared to a Nafion PEM at 30 °C.

25 ENERGY STORAGE↗

Calcium Solubility In Zeolite Synthetic-Apatite Mixtures

Life support systems at a lunar or martian outpost will require the ability to produce food growing in 1) treated lunar or martian regolith; 2) a synthetic soil, or 3) some combination of both. Zeoponic soil, composed of NH4 (-) and K-exchanged clinoptilolite (Cp) and synthetic apatite (Ap), can provide slow-release fertilization via dissolution and ion-exchange. Equilibrium studies indicate that KNH4, P, and Mg are available to plants at sufficient levels, however, Ca is deficient. Ca availability can be increased by adding a second Ca-bearing mineral: calcite (Cal); dolomite (Dol); or wollastonite (Wol). Additions of Cal, Dol, and Wol systematically change the concentrations of Ca and P in solution. Cal has the greatest effect, Dol the least, and Wol is intermediate.

Beiersdorfer, R.↗

The Hard Ferromagnetism in FePS 3 Induced by Non‐Magnetic Molecular Intercalation

Abstract Manipulating the magnetic ground states of 2D magnets is a focal point of recent research efforts. Various methods have demonstrated efficacy in modulating the magnetic properties inherent to van der Waals (vdW) magnetic systems. Herein, the emergence of robust anisotropic ferromagnetism within antiferromagnetic FePS 3 is unveiled via intercalation with non‐magnetic pyridinium ions. A one‐step ion exchange reaction facilitates the formation of energetically favorable B‐phase and metastable P‐phase. Notably, both B‐ and P‐phases manifest hard ferromagnetic behavior, featuring substantial unsaturated coercive fields (>7 T) and high Curie temperatures (72–87 K). First‐principles calculations elucidate the pivotal role of electron transfer from pyridinium ions to FePS 3 in engineering magnetic exchange interactions. Calculated effective spin Hamiltonian corroborates the observed hard ferromagnetism in intercalated FePS 3 . This study offers crucial insights into hard magnetism in intercalated vdW materials, thereby presenting promising avenues for 2D vdW magnet‐based magnetic devices.

Ou, Yunbo↗

Electric propulsion system technology

The work performed in fiscal year (FY) 1991 under the Propulsion Technology Program RTOP (Research and Technology Objectives and Plans) No. (55) 506-42-31 for Low-Thrust Primary and Auxiliary Propulsion technology development is described. The objectives of this work fall under two broad categories. The first of these deals with the development of ion engines for primary propulsion in support of solar system exploration. The second with the advancement of steady-state magnetoplasmadynamic (MPD) thruster technology at 100 kW to multimegawatt input power levels. The major technology issues for ion propulsion are demonstration of adequate engine life at the 5 to 10 kW power level and scaling ion engines to power levels of tens to hundreds of kilowatts. Tests of a new technique in which the decelerator grid of a three-grid ion accelerator system is biased negative of neutralizer common potential in order to collect facility induced charge-exchange ions are described. These tests indicate that this SAND (Screen, Accelerator, Negative Decelerator) configuration may enable long duration ion engine endurance tests to be performed at vacuum chamber pressures an order of magnitude higher than previously possible. The corresponding reduction in pumping speed requirements enables endurance tests of 10 kW class ion engines to be performed within the resources of existing technology programs. The results of a successful 5,000-hr endurance of a xenon hollow cathode operating at an emission current of 25 A are described, as well as the initial tests of hollow cathodes operating on a mixture of argon and 3 percent nitrogen. Work performed on the development of carbon/carbon grids, a multi-orifice hollow cathode, and discharge chamber erosion reduction through the addition of nitrogen are also described. Critical applied-field MPD thruster technical issues remain to be resolved, including demonstration of reliable steady-state operation at input powers of hundreds to thousands of kilowatts, achievement of thruster efficiency and specific impulse levels required for missions of interest, and demonstration of adequate engine life at these input power, efficiency, and specific impulse levels. To address these issues we have designed, built, and tested a 100 kW class, radiation-cooled applied-field MPD thruster and a unique dual-beam thrust stand that enables separate measurements of the applied- and self-field thrust components. We have also initiated the development of cathode thermal and plasma sheath models that will eventually be used to guide the experimental program. In conjunction with the cathode modeling, a new cathode test facility is being constructed. This facility will support the study of cathode thermal behavior and erosion mechanisms, the diagnosis of the near-cathode plasma and the development and endurance testing of new, high-current cathode designs. To facilitate understanding of electrode surface phenomenon, we have implemented a telephoto technique to obtain photographs of the electrodes during engine operation. In order to reduce the background vacuum tank pressure during steady-state engine operation in order to obtain high fidelity anode thermal data, we have developed and are evaluating a gas-dynamic diffuser. A review of experience with alkali metal propellants for MPD thrusters led to the conclusion that alkali metals, particularly lithium, offer the potential for significant engine performance and lifetime improvements. These propellants are also condensible at room temperature, substantially reducing test facility pumping requirements. The most significant systems-level issue is the potential for spacecraft contamination. Subsequent experimental and theoretical efforts should be directed toward verifying the performance and lifetime gains and characterizing the thruster flow field to assess its impact on spacecraft surfaces. Consequently, we have begun the design and development of a new facility to study engine operation with alkali metal propellants.

Brophy, John R.↗

Plant Productivity and Characterization of Zeoponic Substrates after Three Successive Crops of Radish (Raphanus sativus L.)

The National Aeronautics and Space Administration (NASA) has developed a zeolite-based synthetic substrate, termed zeoponics. The zeoponic substrate (consisting of NH4(-) and K-exchanged clinoptilolite, synthetic apatite, and dolomite) provides all of the plant-essential nutrients through mineral dissolution and ion exchange, with only the addition of water. Previous studies have shown high productivity of wheat in zeoponic substrates; however, no experiments have been conducted on other crops. The objective of this study was to determine the productivity and nutrient uptake of radish (Raphanus sativus L.) grown in zeoponic substrates with three successive crops in the same substrate. Radish was chosen because of its sensitivities to NH4(+). Average fresh weights of edible roots were similar for radish grown in zeoponic substrates watered with deionized H2O (10.97 g/plant) and in potting mix control substrate irrigated with nutrient solution (10.92 g/plant). Average fresh weight production of edible roots for radish grown in same zeoponic substrate increased in yield over time with the lowest yield in the first crop (7.10 g/plant) and highest in the third crop (13.90 g/plant). The Ca plant tissue levels in radishes (1.8-2.9 wt. %) grown in zeoponic substrates are lower than the suggested sufficient range of 3.0-4.5 wt. % Ca; however, the Ca level is highest (2.9 wt. %) in radishes grown in the third crop in the same zeoponic substrates. The higher radish yield in the third crop was attributed to a reduction in an NH4(-) induced Ca deficiency that has been previously described for wheat grown in zeoponic substrates. The P levels in plant tissues of radish grown in the zeoponic substrates ranged from 0.94-1.15 wt. %; which is slightly higher than the sufficient levels of 0.3-0.7 wt. %. With the exception of Ca and P, other macronutrient and micronutrient levels in radish grown in zeoponic substrates were well within the recommended sufficient ranges. After three successive crops of radish growth, the zeoponic substrates had 52% of the original NH4(-)N and 78% of the original K remaining on zeolite exchange sites. Zeoponic substrates are capable of long-term productivity of radishes for space.

Gruener, J. E.↗

Phosphate anion-quaternary ammonium ion pair coordinated polymer membranes

Ion exchange membranes materials according to the present disclosure exhibit improved conductivity at low and intermediate relative humidity without sacrificing mechanical strength. Polymers are provided that include a backbone with one or more aryl groups, a halocarbyl group, and a halocarbyl side chain attached to the backbone, wherein the halocarbyl side chain includes a halide separated from the backbone by a hydrocarbyl chain, a hydrocarbyl ring, or combinations thereof. The halide is substituted with a tertiary amine and halide anions are then exchanged with hydroxide anions. The polymers are then contacted with phosphoric acid, which is deprotonated by the hydroxide ions, forming anions which enhance interactions with adjacent quaternary ammonium groups and induce excess phosphoric acid molecules to cluster around those quaternary ammonium groups. The membranes exhibit negligible dopant leaching even at high relative humidity.

Bae, Chulsung↗

Charge exchange lifetimes for ions in the magnetosphere

Latest and best measurements of physical quantities involved in complete calculation of the charge exchange lifetime of mirroring magnetospheric ions are coalesced and summarized. It is critical that the charge exchange lifetimes for ions be known as accurately as possible in order to apply the charge exchange mechanism to ion phenomena within the earth's magnetosphere.

Smith, P. H.↗

Effects of emitting surfaces and trapped ions on the sheath physics and current flow in multidimensional plasma systems

Recent one-dimensional simulations of planar sheaths with strong electron emission have shown that trapping of charge-exchange ions causes transitions from space-charge limited (SCL) to inverse sheaths. However, multidimensional emitting sheath phenomena with collisions remained unexplored, due in part to high computational cost. As such, we developed a novel continuum kinetic code to study the sheath physics, current flow and potential distributions in two-dimensional unmagnetized configurations with emitting surfaces. For small negatively biased thermionic cathodes in a plasma, the cathode sheath can exist in an equilibrium SCL state. The SCL sheath carries an immense density of trapped ions, neutralized by thermoelectrons, within the potential well of the virtual cathode. For further increases of emitted flux, the trapped ion cloud expands in space. The trapped ion space charge causes an increase of thermionic current far beyond the saturation limit predicted by conventional collisionless SCL sheath models without ion trapping. For sufficiently strong emission, the trapped ion cloud consumes the entire 2D plasma domain, forming a mode with globally confined ions and an inverse sheath at the cathode. In situations where the emitted flux is fixed and the bias is swept (e.g. emissive probe), the trapped ions cause a large thermionic current to escape for all biases below the plasma potential. Strong suppression of the thermionic emission, required for the probe to float, only occurs when the probe is above the plasma potential.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Elucidating the Role of CO in the NO Storage Mechanism on Pd/SSZ-13 with in Situ DRIFTS

Pd ion exchanged zeolites emerged as promising materials for the adsorption and oxidation of air pollutants. For low-temperature vehicle exhaust, dispersed Pd ions are able to adsorb NO x even in H 2 O-rich exhaust in the presence of carbon monoxide. In order to understand this phenomenon, changes in Pd ligand environment have to be monitored in-situ. Herein, we directly observe the activation of hydrated Pd ion shielded by H 2 O into a carbonyl-nitrosyl complex Pd 2+ (NO)(CO) in SSZ-13 zeolite. The subsequent thermal desorption of ligands on Pd 2+ (NO)(CO) complex proceeds to nitrosyl Pd 2+ rather than to carbonyl Pd 2+ under various conditions. Thus, CO molecules act as additional ligands to provide alternative pathway through Pd 2+ (NO)(CO) complex with lower energy barrier for accelerating NO adsorption on hydrated Pd 2+ ion, which is kinetically limited in the absence of CO. We further demonstrate that hydration of Pd ions in the zeolite is a prerequisite for CO-induced reduction of Pd ions to metallic Pd. The reduction of Pd ions by CO is limited under dry conditions even at a high temperature of 500°C, while water makes it possible at near RT. However, the primary NO adsorption sites are Pd 2+ ions even in gases containing CO and water. These findings clarify additional mechanistic aspects of the passive NO x adsorption (PNA) process and will help extend the NOx adsorption chemistry in zeolite-based adsorbers to practical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Donnan potential revealed

Selective transport of solutes across a membrane is critical for many biological, water treatment and energy conversion and storage systems. When a charged membrane is equilibrated with an electrolyte, an unequal distribution of ions arises between phases, generating the so-called Donnan electrical potential at the solution/membrane interface. The Donnan potential results in the partial exclusion of co-ion, providing the basis of permselectivity. Although there are well-established ways to indirectly estimate the Donnan potential, it has been widely reported that it cannot be measured directly. Here we report the first direct measurement of the Donnan potential of an ion exchange membrane equilibrated with salt solutions. Our results highlight the dependence of the Donnan potential on external salt concentration and counter-ion valence, and show a reasonable agreement with current theoretical models of IEMs, which incorporate ion activity coefficients. By directly measuring the Donnan potential, we eliminate ambiguities that arise from limitations inherent in current models.

25 ENERGY STORAGE↗

Porous Ceramic Spheres From Cation Exchange Beads

This document is a slide presentation that examines the use of a simple templating process to produce hollow ceramic spheres with a pore size of 1 to 10 microns. Using ion exchange process it was determined that the method produces porous ceramic spheres with a unique structure: (i.e., inner sphere surrounded by an outer sphere.)

Dynys, Fred↗

Synthesis of Butyl-Exchanged Polyoxymethylene Ethers as Renewable Diesel Blendstocks with Improved Fuel Properties

Methyl-terminated polyoxymethylene ethers (MM-POMEs), having the formula CH3O–(CH2O)n–CH3 (n = 3–5), are a high-cetane, low-sooting group of oxygenates that have recently attracted attention as potential diesel blendstocks. Despite these attractive fuel properties, MM-POMEs have shortcomings due to their low energy density and high water solubility. Guided by a computational fuel property assessment for POMEs with longer end-groups, the most promising improvements in the desired compression ignition fuel properties were observed for butyl-terminated POMEs. Here, an acid-catalyzed transacetalization reaction was developed to exchange the methyl end-groups of MM-POMEs (n = 3–6) with butyl end-groups. The reaction utilizes an ion-exchange resin as the acid catalyst at mild reaction conditions of 60 °C and atmospheric pressure. Approximately 100 mL of butyl-exchanged POMEs in the diesel boiling range were produced, enabling laboratory-scale fuel property testing. The butyl-terminated POME mixture possesses the advantaged fuel properties of the parent MM-POMEs (low-soot, high-cetane) while exhibiting improved energy density (lower heating value (LHV) of 30 MJ/kg) and substantially reduced water solubility (7.3 g/L) compared to the parent MM-POME mixture (LHV of 19 MJ/kg , water solubility of 258 g/L).

09 BIOMASS FUELS↗

Pressure Dependence of Insulator-Insulator Contact Charging

The mechanism of insulator-insulator triboelectric (contact) charging is being studied by the Electrostatics and Surface Physics Laboratory at KSC. The hypothesis that surface ion exchange is the primary mechanism is being tested experimentally. A two-phase model based on a small partial pressure of singly charged ions in an ambient ideal gas in equilibrium with a submonolayer adsorbed film will provide predictions about charging as a function Of ion mass, pressure, temperature, and surface adsorption energy. Interactions between ions will be considered in terms of coulombic and screened potential energies. This work is yielding better understanding of the triboelectrification of insulators, which is an important problem in. space exploration technology. The work is also relevant to important industrial processes such as xerography and the application of paints and coatings. Determining a better understanding of the fundamental mechanism of insulator-insulator triboelectrification will hopefully lead to better means of eliminating or at least mitigating its hazards and enhancing its useful applications.

Hogue, Michael D.↗

Achieving High‐Performance and 2000 h Stability in Anion Exchange Membrane Fuel Cells by Manipulating Ionomer Properties and Electrode Optimization

The primary function of the ionomers that are incorporated into fuel cell electrode catalyst layers is to provide pathways for ion transport between the catalyst active sites and the electrolyte. This is influenced by many variables, including the ion-exchange capacity, water uptake, and molecular weight. In anion exchange membrane fuel cells (AEMFCs), controlling ionomer water uptake is particularly important and tailoring this property in each electrode is an important consideration when looking to maximize cell performance. In this study, three poly(norbornene) tetrablock copolymer ionomers with a range of physical properties are synthesized and incorporated into AEMFC anode and cathode electrodes. Systematic electrode engineering with these ionomers allows the peak power density to be increased by 100% (1.6 W cm -2 → 3.2 W cm -2 ) and the current density at 0.2 V to be increased by 59% (5.9 A cm -2 → 9.4 A cm -2 ). Moreover, the top-performing electrode configuration is tested in an operating AEMFC at the US Department of Energy defined current density of 600 mA cm -2 for 2000 h, showing a record-low voltage decay rate of 15.36 µV h -1 – only 3.65% –a over 2000 h. Here, this work sets a new bar for AEMFCs, reporting the best combination of performance and durability of any AEMFC to date.

08 HYDROGEN↗

Solubility and cation exchange in phosphate rock and saturated clinoptilolite mixtures

Mixtures of zeolite and phosphate rock (PR) have the potential to provide slow-release fertilization of plants in synthetic soils by dissolution and ion-exchange reactions. This study was conducted to examine solubility and cation-exchange relationships in mixtures of PR and NH4- and K-saturated clinoptilolite (Cp). Batch-equilibration experiments were designed to investigate the effect of PR source, the proportion of exchangeable K and NH4, and the Cp to PR ratio on solution N, P, K, and Ca concentrations. The dissolution and cation-exchange reactions that occurred after mixing NH4- and K-saturated Cp with PR increased the solubility of the PR and simultaneously released NH4 and K into solution. The more reactive North Carolina (NC) PR rendered higher solution concentrations of NH4 and K when mixed with Cp than did Tennessee (TN) PR. Solution P concentrations for the Cp-NC PR mixture and the Cp-TN PR mixture were similar. Solution concentrations of N, P, K, and Ca and the ratios of these nutrients in solution varied predictably with the type of PR, the Cp/PR ratio, and the proportions of exchangeable K and NH4 on the Cp. Our research indicated that slow-release fertilization using Cp/PR media may provide adequate levels of N, P, and K to support plant growth. Solution Ca concentrations were lower than optimum for plant growth.

NASA Discipline Number 61-10↗

Morphology–Diffusivity Relationships in Fluorine-Free Random Terpolymers for Proton-Exchange Membranes

Here, using atomistic molecular dynamics simulations, we investigate the morphology and transport properties of a new family of fluorine-free terpolymers designed as proton-exchange membranes. Simulated random terpolymers consist of three monomers with a 5-carbon backbone with a phenylsulfonate, phenyl, or no pendant group and have ion exchange capacities (IECs) ranging from 1.06–4.14 mmol/g. At a hydration level of 9, cluster analysis reveals macrophase separation between water and terpolymers with IEC < 2.1 mmol/g and continuous, percolated hydrophilic and hydrophobic nanoscale domains at higher IECs. Channel width distribution analysis of the percolated morphologies revealed that more hydrophobic units produce less uniform channels. Decreasing the surface area per sulfonate group and increasing the fractal dimension of the hydrophilic domains correlate with increased water diffusivity, due to a more acidic interface and more isotropic water channels. Relative to the previously studied phenylsulfonate homopolymer, these terpolymers with lower IECs have only modestly lower water diffusion, and we anticipate other advantages related to processability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗