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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
NASA NTRS1992

Catalysts for ultrahigh current density oxygen cathodes for space fuel cell applications

The objective was to identify promising electrocatalyst/support systems for oxygen cathodes capable of operating at ultrahigh current densities in alkaline fuel cells. Such cells will require operation at relatively high temperatures and O2 pressures. A number of materials were prepared, including Pb-Ru and Pb-Ir pyrochlores, RuO2 and Pt-doped RuO2, lithiated NiO and La-Ni perovskites. Several of these materials were prepared using techniques that had not been previously used to prepare them. Particularly interesting was the use of the alkaline solution technique to prepare Pt-doped and Pb-Ru pyrochlores in high area form. Also interesting was the use of the fusion (melt) method for preparing the Pb-Ru pyrochlore. Several of the materials were also deposited with platinum. Well-crystallized Pb2Ru2O(7-y) was used to fabricate very high performance O2 cathodes with good stability in room temperature KOH. This material was also found to be stable over a useful potential range at approx. 140 C in concentrated KOH. For some of the samples, fabrication of the gas-fed electrodes could not be fully optimized during this project period. Future work may be directed at this problem. Pyrochlores that were not well-crystallized were found to be unstable in alkaline solution. Very good O2 reduction performance and stability were observed with Pb2RuO(7-y) in a carbon-based gas-fed electrode with an anion-conducting membrane placed on the electrolyte side of the electrode. The performance came within a factor of about two of that observed without carbon. High area platinum and gold supported on several conductive metal oxide supports were examined. Only small improvements in O2 reduction performance at room temperature were observed for Pb2Ru2O(7-y) as a support because of the high intrinsic activity of the pyrochlore. In contrast, a large improvement was observed for Li-doped NiO as a support for Pt. Very poor performance was observed for Au deposited on Li-NiO at approx. 150 C. Nearly reversible behavior was observed for the O2/OH(-) couple for Li-doped NiO at approx. 200 C. The temperature dependence for the O2 reduction was examined.

Tryk, Donald A.↗
NASA NTRS2019

Nanopore-Templated Silver Nanoparticle Arrays Photopolymerized in Zero-Mode Wavelengths

In situ fabrication of nanostructures within a solid-polymer electrolyte confined to subwavelength-diameter nanoapertures is a promising approach for producing nanomaterials for nanophotonic and chemical sensing applications. The solid-polymerelectrolyte can be patterned by lithographic photopolymerization of poly(ethyleneglycol) diacrylate (PEGDA)-based silver cation (Ag+)-containing polyelectrolyte. Here, we present a new method for fabricating nanopore-templated Ag nanoparticle (AgNP)arrays by in situ photopolymerization using a zero-mode waveguide (ZMW) array to simultaneously template embedded AgNPs and control the spatial distribution of the optical field used for photopolymerization. The approach starts with an array of nanopores fabricated by sequential layer-by-layer deposition and focused ion beam milling. These structures have an optically transparent bottom, allowing access of the optical radiation to the attoliter-volume ZMW region to photopolymerize a PEGDA monomer solution containing AgNPs and Ag+. The electric field intensity distribution is calculated for various ZMW optical cladding layer thicknesses using finite-element simulations, closely following the light-blocking efficiency of the optical cladding layer. The fidelity of the polyelectrolyte nanopillar pattern was optimized with respect to experimental conditions, including the presence or absence of Ag+ and AgNPs and the concentrations of PEGDA and Ag+. The self-templated approach for photo patterning high-resolution photolabile polyelectrolyte nanostructures directly within a ZMW array could lead to a new class of metamaterials formed by embedding metal nanoparticles within a dielectric in a well-defined spatial array.

Zero-mode waveguide↗
NASA NTRS2006

Li-Ion Batteries for Space Applications: High Specific Energy and Wide-Operating Temperature

Compared to the conventional Ni-Co oxides (with or without AI additions), the NMC (1/3:1/3:1/3) cathode provides marginal improvement in specific capacity. However, some of the formulations based on the solid solutions of layered Li2Mn03 and LiM02 (M = Mn0.5Ni0.5} have shown capacities as high as 250 mAh/g, combined with high cell voltages (4.5 V) and with the likelihood of enhanced thermal stability. Multi-component electrolytes with low EC-proportions and selected co-solvents provide significant improvement in the low temperature performance, down to -60 C, combined with the non-flammable attribute from the co-solvents. The NMC cathode shows good compatibility with the carbonate-based low temperature electrolytes. Impressive performances have been realized at low temperatures of <= 30 C. Electrolytes with high salt concentration and high EC content fare well at room temperatures, while the formulations with low EC content and low salt concentration are preferred at low temperatures. DPA studies reveal increased SEI growth on the electrodes, especially anode, upon irradiation. Performance of low temperature electrolytes in prototype cells corroborate the findings from laboratory cells.

storage↗
NASA NTRS2011

Li-Ion Cells Employing Electrolytes With Methyl Propionate and Ethyl Butyrate Co-Solvents

Future NASA missions aimed at exploring Mars and the outer planets require rechargeable batteries that can operate at low temperatures to satisfy the requirements of such applications as landers, rovers, and penetrators. A number of terrestrial applications, such as hybrid electric vehicles (HEVs) and electric vehicles (EVs) also require energy storage devices that can operate over a wide temperature range (i.e., -40 to +70 C), while still providing high power capability and long life. Currently, the state-of-the-art lithium-ion system has been demonstrated to operate over a wide range of temperatures (-30 to +40 C); however, the rate capability at the lower temperatures is very poor. These limitations at very low temperatures are due to poor electrolyte conductivity, poor lithium intercalation kinetics over the electrode surface layers, and poor ionic diffusion in the electrode bulk. Two wide-operating-temperature-range electrolytes have been developed based on advances involving lithium hexafluorophosphate-based solutions in carbonate and carbonate + ester solvent blends, which have been further optimized in the context of the technology and targeted applications. The approaches employed include further optimization of electrolytes containing methyl propionate (MP) and ethyl butyrate (EB), which are effective co-solvents, to widen the operating temperature range beyond the baseline systems. Attention was focused on further optimizing ester-based electrolyte formulations that have exhibited the best performance at temperatures ranging from -60 to +60 C, with an emphasis upon improving the rate capability at -20 to -40 C. This was accomplished by increasing electrolyte salt concentration to 1.20M and increasing the ester content to 60 percent by volume to increase the ionic conductivity at low temperatures. Two JPL-developed electrolytes 1.20M LiPF6 in EC+EMC+MP (20:20:60 v/v %) and 1.20M LiPF6 in EC+EMC+EB (20:20:60 v/v %) operate effectively over a wide temperature range in MCMB-LiNiCoAlO2 and Li4Ti5O12-LiNi-CoAlO2 prototype cells. These electrolytes have enabled high rate performance at low temperature (i.e., up to 2.0C rates at -50 C and 5.0C rates at -40 C), and good cycling performance over a wide temperature range (i.e., from -40 to +70 C). Current efforts are focused upon improving the high temperature resilience of the methyl propionatebased system through the use of electrolyte additives, which are envisioned to improve the nature of the solid electrolyte interphase (SEI) layers.

Smart, Marshall C.↗
NASA NTRS1995

Hypervolemia from Drinking Hyperhydration Solutions at Rest and Exercise

The mechanism of muscular fatigue from physical work and exercise (high metabolism) is not clear, but involves disturbances of muscle surface membrane excitation-contraction coupling from changes in sarcoplasmic reticulum Ca2+ release, cell H+ and Pi responses, and carbohydrate metabolism. Fatigue in people at rest (low metabolism) involves both psychological and physiological factors, probably in different proportions. One common factor appears to be the level and distribution of water and electrolytes within muscle cells and other vascular, interstitial, body fluid compartments. The vascular fluid volume, composed of plasma and red blood cells, is a primary regulatory factor for cardiovascular function; reduction of vascular volume (hypovolemia) and total body water (hypohydration) adversely affect exercise performance. Plasma volume and plasma ionic-osmotic constituent concentrations are also regulatory factors for body thermoregulation, which is often compromised from exercise induced hypovolemia and hypohydration. Rehydration of dehydrated people on earth is relatively easy with appropriate food (osmols), fluid, and a restful environment. But ad libitum drinking under stressful conditions; e.g., heat, exercise, or prior dehydration, results in involuntary dehydration defined as the delay in full fluid replacement (euhydration) during and following loss of body fluid. Astronauts, with their reduced total body water are euhydrated while in weightlessness, but become "dehydrated" during reentry and landing. Thus, people subjected to acute or chronic stress are probably somewhat "dehydrated" as well as fatigued. Many rehydration drinks are more concentrated (hypertonic-hyperosmotic) with respect to the normal plasma osmolality of 285 mOsm/kg H2O and more of the drink osmols are contributed by carbohydrates than by ionized substances. There have been few studies on the efficacy of various drink formulations for increasing body fluid compartment volumes, especially plasma volume, in rested hydrated subjects. Recent findings from our laboratory have indicated that drinks containing greater concentrations of ionized substances (Performance 1 and AstroAde) up to 157 mEq/L Na+ induced greater levels of hypervolemia in resting, moderately dehydrated men, and were also better than water for attenuating the characteristic hypovolemia during supine, submaximal, leg ergometer exercise.

Greenleaf, John E.↗
NASA NTRSDate not supplied

Considerations on Electrolytic Conductivity Measurement for Monitoring of Ionic Silver Biocide Dosing

NASA interest in ionic silver (Ag+) as a biocide for spacecraft potable water systems motivates the development of Ag+ concentration sensors to ensure nominal dosing. The electrolytic conductivity change of highly-purified potable water is linearly related to the concentration of chemically-dosed Ag+ and could serve as a useful proxy measurement, while the conductivity change during electrolytic dosing may be less so, depending on the influent water chemistry and electrolytic efficiency. Understanding and mitigating the potentially deleterious effects of Ag+ interaction with conductivity measurement systems requires investigation. Issues associated with traditional conductivity cells, which rely on wetted(typically metal or graphite) electrodes, and capacitively-coupled contactless conductivity detection (C4D) for this application are considered. Traditional conductivity cells may potentially be subject to significant excitation-induced or auto-galvanic reduction of Ag+. These may result in Ag+ depletion or electrode fouling and associated measurement error. Proper selection of electrode material, excitation parameters, and cell geometry may limit such effects. C4D uses electrodes placed outside an inert, insulating material, with dielectric polarization enabling the production of an electric field and resultant current across the analyte solution. This approach could potentially mitigate problems with Ag+ depletion and fouling by eliminating the possibility of auto-galvanic deposition and reducing the Faradaic current density. However, it is necessary to confirm C4D performance at very low conductivity levels and to determine if long-term operation produces conductive deposits, which could result in measurement error. A commercial C4D system with 1/16” (1.59 mm)outer diameter flow tubing and claimed performance in the conductivity range appropriate for this application was identified, and its sensitivity in the upper parts of this range was confirmed in a preliminary experiment. A concept for a C4D detector that could allow for full rate flow-through using planar electrodes and thin-film dielectric layers is discussed.

silver↗
NASA NTRSDate not supplied

Monitoring of Ionic Silver Biocide with Capacitively-Coupled Contactless Conductivity Detection (C4D)

Monitoring of biocide dosing in spacecraft potable water systems is desirable to ensure dosing system operation and resultant microbial control. Electrolytic conductivity is linearly related to the concentration ionic silver (Ag+, the baseline biocide for future NASA missions) chemically dosed into highly purified water, and could serve as a proxy measurement. Traditional conductivity cells rely on immersed metal or graphite electrodes, which may potentially be subject to significant current-induced or auto-galvanic deposition of Ag+. Furthermore, oxide fouling may potentially induce measurement errors. Capacitively-coupled contactless conductivity detection (C4D) is a promising alternative. C4D uses electrodes placed outside an inert, non-conductive flow path, potentially mitigating such problems. We identified and purchased a commercial C4D system with claimed performance (conductivity range: 20 nS/cm to 4 µS/cm) appropriate for this application. We characterized the instrument’s performance with conductivity standards and Ag+ solutions. We began investigations considering practical and long-term detector operation, including potential current-induced deposition of conductive deposits at the tubing wall. In addition, we designed a side-stream flow system to provide liquid flow through the narrow tubing (1/16” outer diameter) required by the detector and characterized the performance of the combined C4D detector/flow system. Finally, we completed theoretical modeling of expected conductivity change with multiple dosing techniques and water chemistries.

Lance Dean Delzeit↗
NASA NTRS1989

Advanced double layer capacitors

There is a need for large amounts of power to be delivered rapidly in a number of airborne and space systems. Conventional, portable power sources, such as batteries, are not suited to delivering high peak power pulses. The charge stored at the electrode-electrolyte double layer is, however, much more assessible on a short time scale. Devices exploiting this concept were fabricated using carbon and metal oxides (Pinnacle Research) as the electrodes and sulfuric acid as the electrolyte. The approach reported, replaces the liquid sulfuric acid electrolyte with a solid ionomer electrolyte. The challenge is to form a solid electrode-solid ionomer electrolyte composite which has a high capacitance per geometric area. The approach to maximize contact between the electrode particles and the ionomer was to impregnate the electrode particles using a liquid ionomer solution and to bond the solvent-free structure to a solid ionomer membrane. Ruthenium dioxide is the electrode material used. Three strategies are being pursued to provide for a high area electrode-ionomer contact: mixing of the RuOx with a small volume of ionomer solution followed by filtration to remove the solvent, and impregnation of the ionomer into an already formed RuOx electrode. RuOx powder and electrodes were examined by non-electrochemical techniques. X-ray diffraction has shown that the material is almost pure RuO2. The electrode structure depends on the processing technique used to introduce the Nafion. Impregnated electrodes have Nafion concentrated near the surface. Electrodes prepared by the evaporation method show large aggregates of crystals surrounded by Nafion.

Sarangapani, S.↗
NASA NTRS2000

Effect of hyperosmotic solutions on salt excretion and thirst in rats

We investigated urinary changes and thirst induced by infusion of hyperosmotic solutions in freely moving rats. Intracarotid infusions of 0.3 M NaCl (4 ml/20 min, split between both internal carotid arteries) caused a larger increase in excretion of Na(+) and K(+) than intravenous infusions, indicating that cephalic sensors were involved in the response to intracarotid infusions. Intravenous and intracarotid infusions of hyperosmotic glycerol or urea (300 mM in 150 mM NaCl) had little or no effect, suggesting the sensors were outside the blood-brain barrier (BBB). Intracarotid infusion of hypertonic mannitol (300 mM in 150 mM NaCl) was more effective than intravenous infusion, suggesting that cell volume rather than Na(+) concentration of the blood was critical. Similarly, intracarotid infusion (2 ml/20 min, split between both sides), but not intravenous infusion of hypertonic NaCl or mannitol caused thirst. Hyperosmotic glycerol, infused intravenously or into the carotid arteries, did not cause thirst. We conclude that both thirst and electrolyte excretion depend on a cell volume sensor that is located in the head, but outside the BBB.

NASA Discipline Regulatory Physiology↗
NASA NTRS2019

Electrochemical Solutions for Advanced Life Support

The Oxygen Generating Assembly (OGA) on-board the International Space Station (ISS) employs a polymer electrolyte membrane (PEM) water electrolysis cell stack to electrochemically dissociate water into its two components – oxygen and hydrogen. Oxygen is provided to the cabin atmosphere for crew respiration while the hydrogen is delivered to a carbon dioxide reduction system to recover oxygen as water. The design of the OGA evolved over a number of years to arrive at the system solution that is currently operational on ISS. Future manned missions to space will require advanced technologies that eliminate the need for resupply from earth and feature in-situ resource utilization to sustain crew life and to provide useful materials to the crew. The architects planning such missions should consider all potential solutions at their disposal to arrive at an optimal vehicle solution that minimizes crew maintenance time, launch weight, installed volume and energy consumption demands. Skyre is developing new technologies through funding from NASA, the Department of Energy, and internal investment based on PEM technology that could become an integral part of these new vehicle solutions. At varying stages of Technology Readiness Level (TRL) are: an oxygen concentrator and compressor that can separate oxygen from an air stream and provide an enriched oxygen resource for crew medical use and space suit recharge without any moving parts in the pure oxygen stream; a regenerative carbon dioxide removal system featuring a PEM-based sorbent regenerator; a carbon dioxide reduction system that electrochemically produces organic compounds that could serve as fuels or as a useful intermediary to more beneficial compounds; and an electrochemical hydrogen separator and compressor for hydrogen recycle. The technical maturity of these projects is presented along with pertinent performance test data that could be beneficial in future study efforts.

Roy, Robert J.↗
NASA NTRS2002

Renal responses to plasma volume expansion and hyperosmolality in fasting seal pups

Renal responses were quantified in northern elephant seal (Mirounga angustirostris) pups during their postweaning fast to examine their excretory capabilities. Pups were infused with either isotonic (0.9%; n = 8; Iso) or hypertonic (16.7%; n = 7; Hyper) saline via an indwelling catheter such that each pup received 3 mmol NaCl/kg. Diuresis after the infusions was similar in magnitude between the two treatments. Osmotic clearance increased by 37% in Iso and 252% in Hyper. Free water clearance was reduced 3.4-fold in Hyper but was not significantly altered in Iso. Glomerular filtration rate increased 71% in the 24-h period after Hyper, but no net change occurred during the same time after Iso. Natriuresis increased 3.6-fold in Iso and 5.3-fold in Hyper. Iso decreased plasma arginine vasopressin (AVP) and cortisol acutely, whereas Hyper increased plasma and excreted AVP and cortisol. Iso was accompanied by the retention of water and electrolytes, whereas the Hyper load was excreted within 24 h. Natriuresis is attributed to increased filtration and is independent of an increase in atrial natriuretic peptide and decreases in ANG II and aldosterone. Fasting pups appear to have well-developed kidneys capable of both extreme conservation and excretion of Na(+).

NASA Center ARC↗
NASA NTRS1998

Formation of RNA oligomers on montmorillonite: site of catalysis

Certain montmorillonites catalyze the self condensation of the 5'-phosphorimidazolide of nucleosides in pH 8 aqueous electrolyte solutions at ambient temperatures leading to formation of RNA oligomers. In order to establish the nature of the sites on montmorillonite responsible for this catalytic activity, oligomerization reactions were run with montmorillonites which had been selectively modified (I) at the edges by (a) fluoride treatment, (b) silylation, (c) metaphosphate treatment of the anion exchange sites (II) in the interlayer by (a) saturation with quaternary alkylammonium ions of increasing size, (b) aluminum polyoxo cations. High pressure liquid chromatography, HPLC, analysis of condensation products for their chain lengths and yields indicated that modification at the edges did not affect the catalytic activity to a significant extent, while blocking the interlayer strongly inhibited product formation.

NASA Discipline Exobiology↗
NASA NTRS2008

Special Polymer/Carbon Composite Films for Detecting SO2

A family of polymer/carbon films has been developed for use as sensory films in electronic noses for detecting SO2 gas at concentrations as low as 1 part per million (ppm). Most previously reported SO2 sensors cannot detect SO2 at concentrations below tens of ppm; only a few can detect SO2 at 1 ppm. Most of the sensory materials used in those sensors (especially inorganic ones that include solid oxide electrolytes, metal oxides, and cadmium sulfide) must be used under relatively harsh conditions that include operation and regeneration at temperatures greater than 100 C. In contrast, the present films can be used to detect 1 ppm of SO2 at typical opening temperatures between 28 and 32 C and can be regenerated at temperatures between 36 and 40 C. The basic concept of making sensing films from polymer/carbon composites is not new. The novelty of the present family of polymer/carbon composites lies in formulating the polymer components of these composites specifically to optimize their properties for detecting SO2. First-principles quantum-mechanical calculations of the energies of binding of SO2 molecules to various polymer functionalities are used as a guide for selecting polymers and understanding the role of polymer functionalities in sensing. The polymer used in the polymer-carbon composite is a copolymer of styrene derivative units with vinyl pyridine or substituted vinyl pyridine derivative units. To make a substituted vinyl pyridine for use in synthesizing such a polymer, poly(2-vinyl pyridine) that has been dissolved in methanol is reacted with 3-chloropropylamine that has been dissolved in a solution of methanol. The methanol is then removed to obtain the copolymer. Later, the copolymer can be dissolved in an appropriate solvent with a suspension of carbon black to obtain a mixture that can be cast and then dried to obtain a sensory film.

Homer, Margie↗
NASA NTRS2004

Electrodeionization Using Microseparated Bipolar Membranes

An electrochemical technique for deionizing water, now under development, is intended to overcome a major limitation of prior electrically-based water-purification techniques. The limitation in question is caused by the desired decrease in the concentration of ions during purification: As the concentration of ions decreases, the electrical resistivity of the water increases, posing an electrical barrier to the removal of the remaining ions. In the present technique, this limitation is overcome by use of electrodes, a flowfield structure, and solid electrolytes configured to provide conductive paths for the removal of ions from the water to be deionized, even when the water has already been purified to a high degree. The technique involves the use of a bipolar membrane unit (BMU), which includes a cation-exchange membrane and an anion-exchange membrane separated by a nonconductive mesh that has been coated by an ionically conductive material (see figure). The mesh ensures the desired microseparation between the ion-exchange membranes: The interstices bounded by the inner surfaces of the membranes and the outer surfaces of the coated mesh constitute a flow-field structure that allows the water that one seeks to deionize (hereafter called "process water" for short) to flow through the BMU with a low pressure drop. The flow-field structure is such that the distance between any point in the flow field and an ionically conductive material is small; thus, the flow-field structure facilitates the diffusion of molecules and ions to and from the ion-exchange membranes. The BMU is placed between an anode and a cathode, but not in direct contact with these electrodes. Instead, the space between the anion-exchange membrane and the anode is denoted the anode compartment and is filled with an ionic solution. Similarly, the space between the cation-exchange membrane and the cathode is denoted the cathode compartment and is filled with a different ionic solution. The electrodes are made of titanium coated with platinum.

Lyons, Donald↗
NASA NTRS2004

Direct Electrolytic Deposition of Mats of Mn(x)O(y) Nanowires

Mats of free-standing manganese oxide (MnxOy) nanowires have been fabricated as experimental electrode materials for rechargeable electrochemical power cells and capacitors. Because they are free-standing, the wires in these mats are electrochemically accessible. The advantage of the mat-of-nanowires configuration, relative to other configurations of electrode materials, arises from the combination of narrowness and high areal number density of the wires. This combination offers both high surface areas for contact with electrolytes and short paths for diffusion of ions into and out of the electrodes, thereby making it possible to charge and discharge at rates higher than would otherwise be possible and, consequently, to achieve greater power densities. The nanowires are fabricated in an electrolytic process in which there is no need for an electrode binder material. Moreover, there is no need to incorporate an electrically conductive additive into the electrode material; the only electrically conductive material that must be added is a thin substrate contact film at the anchored ends of the nanowires. Hence, the mass fraction of active electrode material is close to 100 percent, as compared with about 85 percent in conventional electrodes made from a slurry of active electrode material, binder, and conductive additive pressed onto a metal foil. The locations and sizes of the nanowires are defined by holes in templates in the form of commercially available porous alumina membranes. In experiments to demonstrate the present process, alumina membranes of various pore sizes and degrees of porosity were used. First, a film of Au was sputtered onto one side of each membrane. The membranes were then attached, variously, to carbon tape or a gold substrate by use of silver or carbon paste. Once thus attached, the membranes were immersed in a plating solution comprising 0.01 M MnSO4 + 0.03 M (NH4)2SO4. The pH of the solution was kept constant at 8 by addition of H2SO4 or NH4OH as needed. Mn(x)O(y) nanowires were potentiostatically electrodeposited in the pores in the alumina templates. Depending on the anodic deposition potentials, Mn(x)O(y) was deposited in various oxidation states [divalent (Mn3O4), trivalent (Mn2O3), or tetravalent (MnO2)]. The Mn(x)O(y) wires were made free-standing (see figure) by dissolving the alumina templates, variously, in KOH or NaOH at a concentration of 20 volume percent.

Myung, Nosang↗
NASA NTRS2006

Multistage Electrophoretic Separators

A multistage electrophoresis apparatus has been invented for use in the separation of cells, protein molecules, and other particles and solutes in concentrated aqueous solutions and suspensions. The design exploits free electrophoresis but overcomes the deficiencies of prior free-electrophoretic separators by incorporating a combination of published advances in mathematical modeling of convection, sedimentation, electro-osmotic flow, and the sedimentation and aggregation of droplets. In comparison with other electrophoretic separators, these apparatuses are easier to use and are better suited to separation in relatively large quantities characterized in the art as preparative (in contradistinction to smaller quantities characterized in the art as analytical). In a multistage electrophoretic separator according to the invention, an applied vertical steady electric field draws the electrically charged particles of interest from within a cuvette to within a collection cavity that has been moved into position of the cuvette. There are multiple collection cavities arranged in a circle; each is aligned with the cuvette for a prescribed short time. The multistage, short-migration-path character of the invention solves, possibly for the first time, the fluid-instability problems associated with free electrophoresis. The figure shows a prototype multistage electrophoretic separator that includes four sample stations and five collection stages per sample. At each sample station, an aqueous solution or suspension containing charged species to be separated is loaded into a cuvette, which is machined into a top plate. The apparatus includes a lower plate, into which 20 collection cavities have been milled. Each cavity is filled with an electrophoresis buffer solution. For the collection of an electrophoretic fraction, the lower plate is rotated to move a designated collection cavity into alignment with the opening of the cuvette. An electric field is then applied between a non-gassing electrode in the collection cavity and an electrolyte compartment, which is separated from the cuvette by a semipermeable membrane. The electrolyte is refreshed by circulation by use of a peristaltic pump. In subsequent steps, the lower plate is rotated to collect other electrophoretic fractions. Later, the collected fractions are removed from the collection cavities through ports that have threaded plugs. The base of the apparatus contains power supplies and a computer interface. The design includes provisions for monitoring and feedback control of cavity position, electric field, and temperature. The operation of the apparatus can easily be automated, as demonstrated by use of software that has already been written for this purpose.

Thomas, Nathan↗
NASA NTRS2004

New Material for Surface-Enhanced Raman Spectroscopy

A chemical method of synthesis and application of coating materials that are especially suitable for surface-enhanced Raman spectroscopy (SERS) has been developed. The purpose of this development is to facilitate the utilization of the inherently high sensitivity of SERS to detect chemicals of interest (analytes) in trace amounts, without need for lengthy sample preparation. Up to now, the use of SERS has not become routine because the methods available have not been able to reproduce sampling conditions and provide quantitative measurements. In contrast, the coating materials of the present method enable analysis with minimum preparation of samples, and SERS measurements made using these materials are reproducible and reversible. Moreover, unlike in methods investigated in prior efforts to implement SERS, sampling is not restricted to such specific environments as electrolytes or specific solvents. The coating materials of this method are porous glasses, formed in sol-gel processes, that contain small particles of gold or silver metal. Materials of this type can be applied to the sample-contact surfaces of a variety of sampling and sensing devices, including glass slides, glass vials, fiber-optic probes, and glass tubes. Glass vials with their insides coated according to this method are particularly convenient for SERS to detect trace chemicals in solutions: One simply puts a sample solution containing the analyte(s) into a vial, then puts the vial into a Raman spectrometer for analysis. The chemical ingredients and the physical conditions of the sol-gel process have been selected so that the porous glass formed incorporates particles of the desired metal with size(s) to match the wavelength(s) of the SERS excitation laser in order to optimize the generation of surface plasmons. The ingredients and processing conditions have further been chosen to tailor the porosity and polarity of the glass to optimize the sample flow and the interaction between the analyte(s) and the plasmon field that generates Raman photons. The porous silica network of a sol-gel glass creates a unique environment for stabilizing SERS-active metal particles. Relative to other material structures that could be considered for SERS, the porous silica network offers higher specific surface area and thus greater interaction between analyte molecules and metal particles. Efforts to perform SERS measurements with the help of sampling devices coated by this method have been successful. In tests, numerous organic and inorganic chemicals were analyzed in several solvents, including water. The results of the tests indicate that the SERS measurements were reproducible within 10 percent and linear over five orders of magnitude. One measure of the limits of detectability of chemicals in these tests was found to be a concentration of 300 parts per billion. Further development may eventually make it possible to realize the full potential sensitivity of SERS for detecting some analytes in quantities as small as a single molecule.

Farquharson, Stuart↗