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NASA NTRS2001

Sensors for detecting analytes in fluids

Chemical sensors for detecting analytes in fluids comprise first and second conductive elements (e.g., electrical leads) electrically coupled to and separated by a chemically sensitive resistor which provides an electrical path between the conductive elements. The resistor comprises a plurality of alternating nonconductive regions (comprising a nonconductive organic polymer) and conductive regions (comprising a conductive material) transverse to the electrical path. The resistor provides a difference in resistance between the conductive elements when contacted with a fluid comprising a chemical analyte at a first concentration, than when contacted with a fluid comprising the chemical analyte at a second different concentration. Arrays of such sensors are constructed with at least two sensors having different chemically sensitive resistors providing dissimilar such differences in resistance. Variability in chemical sensitivity from sensor to sensor is provided by qualitatively or quantitatively varying the composition of the conductive and/or nonconductive regions. An electronic nose for detecting an analyte in a fluid may be constructed by using such arrays in conjunction with an electrical measuring device electrically connected to the conductive elements of each sensor.

Lewis, Nathan S.↗

NASA NTRS1999

Sensors for detecting analytes in fluids

Lewis, Nathan S.↗

NASA NTRS1998

Sensors for detecting analytes in fluids

Lewis, Nathan S.↗

NASA NTRS1996

Sensor arrays for detecting analytes in fluids

Chemical sensors for detecting analytes in fluids comprise first and second conductive elements (e.g. electrical leads) electrically coupled to and separated by a chemically sensitive resistor which provides an electrical path between the conductive elements. The resistor comprises a plurality of alternating nonconductive regions (comprising a nonconductive organic polymer) and conductive regions (comprising a conductive material) transverse to the electrical path. The resistor provides a difference in resistance between the conductive elements when contacted with a fluid comprising a chemical analyte at a first concentration, than when contacted with a fluid comprising the chemical analyte at a second different concentration. Arrays of such sensors are constructed with at least two sensors having different chemically sensitive resistors providing dissimilar such differences in resistance. Variability in chemical sensitivity from sensor to sensor is provided by qualitatively or quantitatively varying the composition of the conductive and/or nonconductive regions. An electronic nose for detecting an analyte in a fluid may be constructed by using such arrays in conjunction with an electrical measuring device electrically connected to the conductive elements of each sensor.

Lewis, Nathan S.↗

NASA NTRS2013

New Class of Flow Batteries for Terrestrial and Aerospace Energy Storage Applications

Future sustainable energy generation technologies such as photovoltaic and wind farms require advanced energy storage systems on a massive scale to make the alternate (green) energy options practical. The daunting requirements of such large-scale energy systems such as long operating and cycle life, safety, and low cost are not adequately met by state-of-the-art energy storage technologies such as vanadium flow cells, lead-acid, and zinc-bromine batteries. Much attention is being paid to redox batteries specifically to the vanadium redox battery (VRB) due to their simplicity, low cost, and good life characteristics compared to other related battery technologies. NASA is currently seeking high-specific- energy and long-cycle-life rechargeable batteries in the 10-to-100-kW range to support future human exploration missions, such as planetary habitats, human rovers, etc. The flow batteries described above are excellent candidates for these applications, as well as other applications that propose to use regenerative fuel cells. A new flow cell technology is proposed based on coupling two novel electrodes in the form of solvated electron systems (SES) between an alkali (or alkaline earth) metal and poly aromatic hydrocarbons (PAH), separated by an ionically conducting separator. The cell reaction involves the formation of such SES with a PAH of high voltage in the cathode, while the alkali (or alkaline earth metal) is reduced from such an MPAH complex in the anode half-cell. During recharge, the reactions are reversed in both electrodes. In other words, the alkali (alkaline earth) metal ion simply shuttles from one M-PAH complex (SES) to another, which are separated by a metal-ion conducting solid or polymer electrolyte separator. As an example, the concept was demonstrated with Li-naphthalene//Li DDQ (DDQ is 2,3-Dichloro-5,6-dicyano- 1,4-benzoquinone) separated by lithium super ion conductor, either ceramic or polymer (solid polymer or gel polymer) electrolytes. The reactants are Li-naphthalene dissolved in tetrahydrofuran (THF) with a lithium salt of 1M LiBF4 (lithium tetra fluoroborate) in the anode compartment, and DDQ again dissolved in THF and also containing 1M LiBF4 salt in the cathode half-cell. The solid electrolyte separator used in the first set of experiments is a ceramic solid electrolyte, available from a commercial source. The open circuit voltage of the cells is close to 3.0 V, as expected from the individual half-cell voltages of Li-naphthalene and Li-DDQ. Upon discharge, the cell shows steady discharge voltage of 2.7 V, which confirms that the electrochemical processes do involve lithium ion shuttling from the anodic compartment to the cathode half-cell. The reversibility or rechargeability is demonstrated by charging the partially discharged cells (i.e., with lithium present in the DDQ half). Once again, a steady voltage close to 3.0 V was observed during charge, indicating that the system is quite reversible. In the subsequent concept-demonstration studies, the ceramic electrolyte has been replaced with a gel polymer electrolyte, e.g., PVDF-HFP (poly vinylene difluoride hexafluoropropene) gel, which has several advantages such as high ionic conductivity (almost comparable to liquid electrolyte and about 2 orders of magnitude better than the ceramic equivalent), lower cost, and possibly higher chemical stability at the anode. In addition, it can be bonded to the electrode by thermal fusion to form membrane electrode assemblies (MEAs), as is done in fuel cells.

Bugga, Ratnakumar V.↗

NASA NTRS1977

Materials and techniques for spacecraft static charge control

An overview of the design, development, fabrication, and testing of transparent conductive coatings and conductive lattices deposited or formed on high resistivity spacecraft dielectric materials to obtain control static charge buildup on spacecraft external surfaces is presented. Fabrication techniques for the deposition of indium/tin oxide coatings and copper grid networks on Kapton and FEP Teflon films and special frit coatings for OSR and solar cell cover glasses are discussed. The techniques include sputtering, photoetching, silkscreening, and mechanical processes. A facility designed and built to simulate the electron plasma at geosynchronous altitudes is described along with test procedures. The results of material characterizations as well as electron irradiation aging effects in this facility for spacecraft polymers treated to control static charge are presented. The data presents results for electron beam energies up to 30 kV and electron current densities of 30 nA/cm squared. Parameters measured include secondary emission, surface leakage, and through the sample currents as a function of primary beam energy and voltage.

Amore, L. J.↗

NASA NTRS1985

Mechanical properties testing of candidate polymer matrix materials for use in high performance composites

The mechanical properties of four candidate neat resin systems for use in graphite/epoxy composites are characterized. This includes tensile and shear stiffnesses and strengths, coefficients of thermal and moisture expansion, and fracture toughness. Tests are conducted on specimens in the dry state and moisture-saturated, at temperatures of 23C, 82C and 121C. The neat resins tested are Hexcel HX-1504, Narmco 5245-C, American Cyanamid CYCOM 907, and Union Carbide ERX-4901A (MDA). Results are compared with those obtained for four other epoxy resins tested in a prior program, i.e., Hercules 3502, 2220-1, and 2220-3, and Ciba-Geigy Fibredux 914, as well as with available Hercules 3501-6 data. Scanning electron microscopic examination of fracture surfaces is performed to permit the correlation of observed failure modes with the environmental test conditions. A finite element micromechanics analysis is used to predict unidirectional composite response under various test conditions, using the measured neat resin properties as input data.

Zimmerman, R. S.↗

NASA NTRS2019

Applications of Atomic Layer Deposition in the Modification of Carbon Nanotubes

Atomic Layer Deposition (ALD) is a cost-effective nanoadditive-manufacturing technique that allows for conformal coating of substrates with atomic control in a benign temperature and pressure environment. Using paired precursor gases, thin films can be deposited on flat or textured surfaces ranging from glass, polymers, aerogels, and metals. Through atomic layer control, where single layers of atoms are deposited, fabrication of metal transparent films, nano-laminates, and coatings of nano-channels and pores is achievable. Reaction mechanisms in ALD are normally self-limiting, allowing for atomically accurate control of nanometer (nm) thicknesses. Therefore, high uniformity and precise thickness control make ALD an attractive process for the creation of novel nano-scale devices. Decreases in resistivity and density of electrical wire are needed to improve the function of electronics, electric motors and cables. Such improvements may be accomplished by adding ballistically conducting, metallic carbon nanotubes (CNT) to Cu. ALD was used to coat multiple substrates including CNT with Cu in an effort to make CNT-Cu composites which is more conductive and less dense than Cu. In addition, ALD can be used to as a method to deposit the catalyst layer seed layer for CNT growth using Ni. The ALD of copper metallic films can follow multiple reaction pathways depending on the ALD precursors used. For this work the reaction pathway was deposition of copper oxide and then post process annealing in a hydrogen environment. Copper(II) diacetylacetonate (Cu(acac)2) and ozone are used as precursors for copper oxide. As-deposited copper oxide films prepared at 180°C resulted in a growth per cycle of 1.0 A/cycle with low film resistivity.

Dwivedi, Vivek H.↗

NASA NTRSDate not supplied

Rational Design of Nanoplasmonic Array Geometries for Biosensing

Background: Molecular diagnostics provide early and accurate diagnosis, which is essential for the prevention and treatment of infectious as well as chronic diseases. These tests are designed to detect disease-specific bioanalytes such as nucleic acid (DNA or RNA) or protein (antigens, antibodies) biomarkers. In the context of infectious disease diagnosis, nucleic acid-based detection methods are known to provide more specific and sensitive results. Here, the presence of a unique sequence belonging to the pathogenic genomic material is targeted to identify species, organism, genera and/or antimicrobial resistant gene markers. The majority of the common nucleic acid based diagnostic techniques require amplification (polymerase chain reaction, isothermal amplification etc.) of the pathogenic genetic material prior to detection impacting diagnostic speed, complexity, and cost thereby limiting ease of use. Thus, the development of simplified nucleic acid-based diagnostics that can be even used in resource-poor settings may hugely benefit patients across the globe. Nanopath is a molecular diagnostics company utilizing a solid-state nanosensor to enable sequence-specific detection of target nucleic acids without the need of amplification. These nanostructures enable ultra-sensitive biomarker detection using geometric, feature-dependent properties highly dependent on the local dielectric environment, allowing them to be sensitive to low concentration binding events. This paper describes an application of this approach to provide highly relevant clinical information within a single doctor’s office visit. Intro: The Nanopath team is in collaboration with NASA (National Aeronautics and Space Administration) and NIST (National Institute of Standards and Technology) to push the bounds of the fundamental physics associated with their biosensing platform. The ability of metals to support electromagnetic surface waves gives rise to surface plasmons when optically illuminated. This property, and its strong sensitivity to changes in the local refractive index, allows for the use of metal nanoparticles as ultra-sensitive transducers. In prior work by members of this team, ensembles of randomly oriented nanoparticles (i.e., colloidal nanorods dispersed on chip) were employed for sequence-specific nucleic acid sensing (1-3). While these particle sensors have the advantage of rapid fabrication, they suffer from low sensitivity and quality factor due to the random particle dispersity. In contrast, in this study we employ ordered array nanoparticle ensembles which can be used to improve sensor sensitivity and figure-of-merit. Study Methods Overview: In this talk, we detail the results of sensing experiments and computational simulations to outline a rational design of the structure of these plasmonic nanoparticle arrays for biomolecular sensing. Through simulation and experiment, we iteratively tailor nanostructure dimension to provide high quality signal and large resonance shifts upon modeled nucleic acid binding. In particular, full-wave electromagnetic simulations were conducted using Lumerical photonic simulation software in which periodic boundary conditions were applied in the x- and y- dimensions for each of the nanoplasmonic sensor geometries. To simulate the resonance response to changes in the bulk solution in contact with the sensor surface, the refractive index of the surrounding media was changed appropriately. Nucleic acid hybridization events were modeled using either using spherical structures approximating the relevant radius of genomic material as estimated by polymer models, or as conformal layers with the known refractive indices for nucleic acids. On the basis of initial simulations, nanosensors were fabricated using traditional electron-beam lithography protocols at NIST. To evaluate consensus between simulations and experiments, bulk sensing experiments were carried out in which the resonance peaks were obtained by submerging the sensors in refractive index standards. Key nanosensor characteristics including resonance peak locations, resonance peak shifts as a function of refractive index, and figure of merit (FOM) of extinction curves were examined between the experimental and simulation results prior to proceeding with simulations on additional geometries and more complex solution conditions, and further device fabrication. This iterative process is repeated toward a rational design of nanoplasmonic array geometries for biosensing optimizing response for targeted disease detection. In summary, this study puts forth a methodology for rational design and characterization of regularly spaced nanoparticle arrays for optics-based biosensing. The results of this study will allow for more informed design of nanostructure geometries towards sequence-specific nucleic acid detection. These improved designs have the potential to improve clinical sensitivity and limit-of-detection across disease indication.

sensor↗

NASA NTRS2016

Additive Manufacturing of Silicon Carbide-Based Ceramic Matrix Composites: Technical Challenges and Opportunities

Advanced SiC-based ceramic matrix composites offer significant contributions toward reducing fuel burn and emissions by enabling high overall pressure ratio (OPR) of gas turbine engines and reducing or eliminating cooling air in the hot-section components, such as shrouds, combustor liners, vanes, and blades. Additive manufacturing (AM), which allows high value, custom designed parts layer by layer, has been demonstrated for metals and polymer matrix composites. However, there has been limited activity on additive manufacturing of ceramic matrix composites (CMCs). In this presentation, laminated object manufacturing (LOM), binder jet process, and 3-D printing approaches for developing ceramic composite materials are presented. For the laminated object manufacturing (LOM), fiber prepreg laminates were cut into shape with a laser and stacked to form the desired part followed by high temperature heat treatments. For the binder jet, processing optimization was pursued through silicon carbide powder blending, infiltration with and without SiC nano powder loading, and integration of fibers into the powder bed. Scanning electron microscopy was conducted along with XRD, TGA, and mechanical testing. Various technical challenges and opportunities for additive manufacturing of ceramics and CMCs will be presented.

ceramic matrix composites↗

NASA NTRS2007

Comparison of the Atomic Oxygen Erosion Depth and Cone Height of Various Materials at Hyperthermal Energy

Atomic oxygen readily reacts with most spacecraft polymer materials exposed to the low Earth orbital (LEO) environment. If the atomic oxygen arrival comes from a fixed angle of impact, the resulting erosion will foster the development of a change in surface morphology as material thickness decreases. Hydrocarbon and halopolymer materials, as well as graphite, are easily oxidized and textured by directed atomic oxygen in LEO at energies of approx.4.5 eV. What has been curious is that the ratio of cone height to erosion depth is quite different for different materials. The formation of cones under fixed direction atomic oxygen attack may contribute to a reduction in material tensile strength in excess of that which would occur if the cone height to erosion depth ratio was very low because of greater opportunities for crack initiation. In an effort to understand how material composition affects the ratio of cone height to erosion depth, an experimental investigation was conducted on 18 different materials exposed to a hyperthermal energy directed atomic oxygen source (approx.70 eV). The materials were first salt-sprayed to provide microscopic local areas that would be protected from atomic oxygen. This allowed erosion depth measurements to be made by scanning microscopy inspection. The polymers were then exposed to atomic oxygen produced by an end Hall ion source that was operated on pure oxygen. Samples were exposed to an atomic oxygen effective fluence of 1.0x10(exp 20) atoms/sq cm based on Kapton H polyimide erosion. The average erosion depth and average cone height were determined using field emission scanning electron microscopy (FESEM). The experimental ratio of average cone height to erosion depth is compared to polymer composition and other properties.

Waters, Deborah L.↗

NASA NTRS1998

Effects of Heat Treatment on the Magnetic Properties of Polymer-Bound Iron Particle Cores

Spherical iron particles of three different size distributions, 6-10 microns in diameter, 100 mesh and 30-80 mesh, were mixed with 2.0 wt. % of soluble imide and compression molded at 300 C under 131 MPa. Post fabrication heat treatments were performed at 960 C for 6 hours resulting in a significant enhancement of the permeability in low field region for all the specimens except for the one made of 30-80 mesh particles. The rate of core loss of these specimens at a magnetic induction of 5 kG measured up to 1 kHz shows a noticeable increase after heat treatment which, along with the permeability enhancement, can be explained by the coalescence of particles forming a network of conductivity paths in the specimens. The scanning electron micrographs taken for the 6-10 micron particle specimens show no evidence of heat treatment-induced grain growth. The untreated specimens show a very weak f(sup 2) dependence of the core loss which clearly indicates a negligible contribution from the eddy current loss. In particular, an almost perfect linearity was found in the frequency dependence of the core loss of the untreated specimen made of 100 mesh iron particles.

Namkung, M.↗

NASA NTRS1998

Effects of Heat Treatment on the Magnetic Properties of Polymer-Bound Iron Particle Cores

Spherical iron particles of three different size distributions, 6-10 micrometers in diameter, 100 mesh and 30-80 mesh, were mixed with 2.0 wt % of soluble imide and compression molded at 300 C under 131 MPa. Post-fabrication heat treatments were performed at 960 C for 6 h resulting in a significant enhancement of the permeability in low field region for all the specimens except for the one made of 30-80 mesh particles. The rate of core loss of these specimens at a magnetic induction of 5 kG measured up to 1 kHz shows a noticeable. increase after heat treatment which, along with the permeability enhancement, can be explained by the coalescence of particles forming a network of conductivity paths in the specimens. ne scanning electron micrographs taken for the 6-10 micrometer particle specimens show no evidence of heat treatment-induced grain growth. The untreated specimens show a very weak f(sup 2) -dependence of the core loss which clearly indicates a negligible contribution from the eddy current loss. In particular, an almost perfect linearity was found in the frequency dependence of the core loss of the untreated specimen made of 100 mesh iron particles.

Namkung, M.↗

NASA NTRS2004

Nano-casted Metal Oxide Aerogels as Dual Purpose Structural Components for Space Exploration

NASA missions and space exploration rely on strong, ultra lightweight materials. Such materials are needed for building up past and present space vehicles such as the Sojourner Rover (1997) or the two MERs (2003), but also for a number of components and/or systems including thermal insulators, Solar Sails, Rigid Aeroshells, and Ballutes. The purpose of my internship here at Glenn Research Center is to make dual purpose materials; materials that in addition to being lightweight have electronic, photophysical and magnetic properties and, therefore, act as electronic components and sensors as well as structural components. One type of ultra lightweight material of great interest is aerogels, which have densities ranging from 0.003 g/cc to 0.8 g/cc . However, aerogels are extremely fragile and, as a result, have limited practical applications. Recently, Glenn Research Center has developed a process of nano-casting polymers onto the inorganic network of silica-based aerogels increasing the strength 300 fold while only increasing the density 3 fold. By combining the process of nano-casting polymers with inorganic oxide networks other than silica, we are actively pursuing lightweight dual purpose materials. To date, thirty different inorganic oxide aerogels have been prepared using either standard sol-gel chemistry or a non-alkoxide method involving metal chloride precursors and an epoxide; epichlorohydrin, propylene oxide or trimethylene oxide, as proton scavengers. More importantly, preliminary investigations show that the residual surface hydroxyl groups on each of these inorganic oxide aerogels can be successfully crosslinked with urethane. In addition to characterizing physical and mechanical properties such as density, strength and flexibility, each of these metal oxide aerogels are being characterized for thermal and electronic conductivity and magnetic and optical properties.

Vassilaras, Plousia E.↗

NASA NTRS1985

Accommodation requirements for microgravity science and applications research on space station

Scientific research conducted in the microgravity environment of space represents a unique opportunity to explore and exploit the benefits of materials processing in the virtual abscence of gravity induced forces. NASA has initiated the preliminary design of a permanently manned space station that will support technological advances in process science and stimulate the development of new and improved materials having applications across the commercial spectrum. A study is performed to define from the researchers' perspective, the requirements for laboratory equipment to accommodate microgravity experiments on the space station. The accommodation requirements focus on the microgravity science disciplines including combustion science, electronic materials, metals and alloys, fluids and transport phenomena, glasses and ceramics, and polymer science. User requirements have been identified in eleven research classes, each of which contain an envelope of functional requirements for related experiments having similar characteristics, objectives, and equipment needs. Based on these functional requirements seventeen items of experiment apparatus and twenty items of core supporting equipment have been defined which represent currently identified equipment requirements for a pressurized laboratory module at the initial operating capability of the NASA space station.

Uhran, M. L.↗

NASA NTRS1989

Electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation (1,2). Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium). A possible approach to this problem is to immobilize the pyrochlore catalyst within an ionic-conducting solid polymer, which would replace the fluid electrolyte within the porous gas diffusion O2 electrode. For bulk alkaline electrolyte, an anion-exchange polymer is needed with a transference number close to unity for the Oh(-) ion. Preliminary short-term measurements with lead ruthenates using a commercially available partially-fluorinated anion-exchange membrane as an overlayer on the porous gas-fed electrode indicate lower anodic polarization and virtually unchanged cathodic polarization.

Prakash, Jai↗

NASA NTRS1981

Two-dimensiosnal electron beam charging model for polymer films

A two dimensional model was developed to describe the charging of thin polymer films exposed to a uniform mon-energetic electron beam. The study was motivated by observed anomalous behavior of geosynchronous satellites which was attributed to electrical discharges associated with the differential charging of satellite surfaces of magnetospheric electrons. Electric fields both internal and external to the irradiated specimen were calculated at steady state in order to identify regions of high electrical stress. Particular emphasis was placed on evaluating the charging characteristics near the material's edge. The model was used to identify and quantify the effects of some of the experimental parameters notably: beam energy; beam angle of incidence; beam current density; material thickness; and material width. Simulations of the following situations were also conducted: positive or negative precharging over part of the surface; a central gap in the material; and a discontinuity in the material's thickness.

Reeves, R. D.↗

NASA NTRS2004

New High-Temperature Membranes Developed for Proton Exchange Membrane Fuel Cells

Fuel cells are receiving a considerable amount of attention for potential use in a variety of areas, including the automotive industry, commercial power generation, and personal electronics. Research at the NASA Glenn Research Center has focused on the development of fuel cells for use in aerospace power systems for aircraft, unmanned air vehicles, and space transportation systems. These applications require fuel cells with higher power densities and better durability than what is required for nonaerospace uses. In addition, membrane cost is a concern for any fuel cell application. The most widely used membrane materials for proton exchange membrane (PEM) fuel cells are based on sulfonated perfluorinated polyethers, typically Nafion 117, Flemion, or Aciplex. However, these polymers are costly and do not function well at temperatures above 80 C. At higher temperatures, conventional membrane materials dry out and lose their ability to conduct protons, essential for the operation of the fuel cell. Increasing the operating temperature of PEM fuel cells from 80 to 120 C would significantly increase their power densities and enhance their durability by reducing the susceptibility of the electrode catalysts to carbon monoxide poisoning. Glenn's Polymers Branch has focused on developing new, low-cost membranes that can operate at these higher temperatures. A new series of organically modified siloxane (ORMOSIL) polymers were synthesized for use as membrane materials in a high-temperature PEM fuel cell. These polymers have an organic portion that can allow protons to transport through the polymer film and a cross-linked silica network that gives the polymers dimensional stability. These flexible xerogel polymer films are thermally stable, with decomposition onset as high as 380 C. Two types of proton-conducting ORMOSIL films have been produced: (1) NASA-A, which can coordinate many highly acid inorganic salts that facilitate proton conduction and (2) NASA-B, which has been produced and which incorporates strongly acidic (proton donating) functional groups into the polymer backbone. Both of these polymer films have demonstrated significantly higher proton conductivity than Nafion at elevated temperatures and low relative humidities. An added advantage is that these polymers are very inexpensive to produce because their starting materials are commodity chemicals that are commercially available in large volumes.

Kinder, James D.↗